Bodywashes containing additives

ABSTRACT

The invention encompasses bodywashes containing an additive. The additive may contain a sunscreen. The additive may contain 2, 3, or more than three sunscreens. Optionally, one or more of the sunscreens may be encapsulated. The invention further encompasses methods of making and using bodywashes containing an additive, e.g., an additive containing a sunscreen.

CROSS-REFERENCE

This application is a continuation of U.S. patent application Ser. No.11/076,517, filed Mar. 8, 2005 now U.S. Pat. No. 6,998,113 and relatedU.S. patent application Ser. No. 11/076,565, filed Mar. 8, 2005 now U.S.Pat. No. 7,001,592 and Ser. No. 11/076,089, filed Mar. 8, 2005 now U.S.Pat. No. 7,037,513 and Ser. No. 11/076,088, filed Mar. 8, 2005 now U.S.Pat. No. 7,052,952 and Ser. No. 11/076,507, filed Mar. 8, 2005 and whichclaims benefit of Provisional Application No. 60/648,961, filed Jan. 31,2005, all of which are incorporated by reference herein in theirentirety.

BACKGROUND OF THE INVENTION

Exposure to ultraviolet light, primarily through exposure to the sun'srays, produces a number of harmful effects including premature skinaging, loss of elasticity, wrinkling, drying, and an increased risk ofdeveloping skin cancer. Currently a number of sunscreen products aremarketed to protect against these harmful effects. All of these productscontain agents known to filter out some of the sun's harmful raysincorporated into creams, ointments, lotions, solutions or suspensions.Such products are applied just prior to anticipated sun exposure,provide short term protection, and are removed by bathing, washing ornormal desquamation of skin. Soap in the form of bodywash has for yearsbeen used to remove oil due to its surfactant composition and associatedcharges. A normal soap contains both charges of a positive and negativenature. Although attempts have been made to combine sunscreens withsoaps (i.e., surfactant agents), none has provided an ideal combinationof high sun protection factor (SPF) and long-lasting effect in acomposition that maintains its integrity. Other additives in addition tosunscreen are also potentially useful when applied in conjunction with abodywash, but at present few products utilize this potential. Thecurrent invention addresses these lacks.

SUMMARY OF THE INVENTION

The invention encompasses bodywashes containing an additive. Theadditive may contain a sunscreen. The invention further encompassesmethods of making and using bodywashes containing an additive, e.g., anadditive containing a sunscreen.

In one aspect, the invention provides a bodywash containing an additivethat comprises a sunscreen, wherein after a single application of thebodywash to skin and rinsing, the skin is protected from sunlight withan average SPF of at least about 15. In some embodiments, the SPF of 15is maintained for an average of at least about 4 hours after rinsing. Insome embodiments, the sunscreen is encapsulated, e.g., in sol-gelmicrocapsules. In some embodiments, the sunscreen is an organicsunscreen that is aminobenzoic acid, avobenzone, cinoxate, dioxybenzone,homosalate, menthyl anthranilate, octocrylene, octyl methoxycinnamate,octyl salicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonicacid, sulisobenzone, or trolamine salicylate. In some embodiments, thesunscreen is a cinnamate derivative. In some embodiments, the additivecontains 3 organic sunscreens. In some embodiments the 3 organicsunscreens are selected from the group consisting of aminobenzoic acid,avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate,octocrylene, octyl methoxycinnamate, octyl salicylate, oxybenzone,padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, andtrolamine salicylate. Embodiments may further contain an inorganicsunscreen. In some embodiments, the inorganic sunscreen is selected fromthe group consisting of zinc oxide and titanium dioxide. In someembodiments, the sunscreen is a UVB absorber sunscreen, and thecomposition also contains a UVA absorber sunscreen and a physicalblocker sunscreen, where the UVB-absorber sunscreen is selected from thegroup consisting of aminobenzoic acid, cinoxate, dioxybenzone,homosalate, octocrylene, octyl methoxycinnamate, octyl salicylate,oxybenzone, padimate O, phenylbenzimidazole sulfonic acid,sulisobenzone, and trolamine salicylate; the UVA-absorber sunscreen isselected from the group consisting of avobenzone and menthylanthranilate; and the physical blocker sunscreen is selected from thegroup consisting of titanium dioxide and zinc oxide. Embodiments mayfurther contain a cationic polymer. In some embodiments, the cationicpolymer is a polyquaternium. In some embodiments, the polyquaternium ispolyquaternium-4, -7, -11, -22, -27, -44, -51, or -64. In preferredembodiments, the cationic polymer is polyquaternium-4. Embodiments mayalso contain a film former, a preservative, and/or an antioxidant thatis stable upon exposure to sunlight.

In another aspect, the invention provides a bodywash containing anadditive that contains a sunscreen, where, after application of thebodywash to skin and rinsing, the sunscreen penetrates an average of nofurther than 30 microns into the skin after application followed byrinsing. In some embodiments of this aspect, after application of thebodywash to skin and rinsing, the skin is protected from sunlight withan average SPF of at least about 15.

In a further aspect, the invention provides a bodywash comprising aUVA-absorbing sunscreen, a UVB-absorbing sunscreen, a physical blockersunscreen, and a cationic polymer. In some embodiments, the UVB-absorbersunscreen is selected from the group consisting of aminobenzoic acid,cinoxate, dioxybenzone, homosalate, octocrylene, octyl methoxycinnamate,octyl salicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonicacid, sulisobenzone, and trolamine salicylate; the UVA-absorbersunscreen is selected from the group consisting of avobenzone andmenthyl anthranilate; the physical blocker sunscreen is selected fromthe group consisting of titanium dioxide and zinc oxide; and thecationic polymer is a polyquaternium. Some of these embodiments containoctyl methoxycinnamate, octocrylene, avobenzone, titanium dioxide, and apolyquaternium selected from the group consisting of polyquaternium-4,-7, -11, -22, -27, -44, -51, or -64. A preferred polyquaternium ispolyquaternium-4. The octylmethoxy cinnamate may be encapsulated, e.g.,in sol-gel microcapsules. The octyl methoxycinnamate can present atabout 4.5–9%, the octocrylene can present at about 0.5-15%, theavobenzone can present at about 2–4%, and the titanium dioxide canpresent at about 3–9%. Additionally, in embodiments containingpolyquaternium-4, the polyquaternium-4 can be present at about 0.5–3%.In some embodiments, the octyl methoxycinnamate is present at about7.6%, the octocrylene is present at about 11.3%, the avobenzone ispresent at about 2.8%, and the titanium dioxide is present at about6.5%. Additionally, in these embodiments that contain polyquaternium-4,the polyquaternium-4 can be present at about 2.8%. A film former canalso be present, e.g., at about 1.5%. In this aspect, the bodywash ofclaim can further contain a non-sunscreen active. In some embodiments,the non-sunscreen active is selected from the group consisting ofsteroidal anti-inflammatory actives, analgesic actives, antifungals,antibacterials, and antiparasitics, anti-allergenics, medicinal actives,skin rash, skin disease and dermatitis medications, insect repellantactives, antioxidants, hair growth promoter, hair bleaching agents,deodorant compounds, and mixtures and combinations thereof. In someembodiments, at least one of the sunscreens is encapsulated, e.g., insol-gel microcapsules. In some embodiments, the cationic polymer is apolyquaternium. In some embodiments, the polyquaternium ispolyquaternium-4, -7, -11, -22, -27, -44, -51, or -64. In preferredembodiments, the cationic polymer is polyquaternium-4. Embodiments mayalso contain a film former, a preservative, and/or an antioxidant thatis stable upon exposure to sunlight.

INCORPORATION BY REFERENCE

All publications and patent applications mentioned in this specificationare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually indicated to be incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention encompasses compositions containing one or moreactive ingredients (also referred to herein as “actives”) that may beadded to a bodywash composition to provide an active/bodywashcombination. The invention also encompasses a bodywash containing suchan active ingredient. In some embodiments, the active ingredient is oneor more sunscreens. The invention further encompasses methods of use andmanufacture of the compositions, and business methods.

As used herein, “bodywash” encompasses all cleansing vehicles applied tothe body. Exemplary forms of cleansing vehicles include, but are notlimited to, liquid, bar, gel, foam, aerosol or pump spray, cream,lotion, stick, powder, or incorporated into a patch or a towelette. Inaddition, soapless cleansers may be used as well. The bodywash can bemade into any suitable product form. Thus, as used herein, “bodywash”includes, but is not limited to, a soap including liquid and bar soap; ashampoo; a hair conditioner; a shower gel; including an exfoliatingshower gel; a foaming bath product (e.g. gel, soap or lotion); a milkbath; a soapless cleanser, including a gel cleanser, a liquid cleanserand a cleansing bar; moist towelletes; a body lotion; a body spray, mistor gel; bath effervescent tablets (e.g., bubble bath); a hand and nailcream; a bath/shower gel; a shower cream; a depilatory cream; a shavingproduct e.g. a shaving cream, gel, foam or soap, an after-shave,after-shave moisturizer; and combinations thereof, and any othercomposition used for cleansing or post-cleansing application to thebody, including the skin and hair. Especially useful as bodywashes inthe invention are soaps, e.g., liquid soaps and bar soaps, and shampoos.

I. Compositions

In one aspect, the invention provides additives containing activeingredients, where the additive is designed to be added to a bodywash(e.g., soap or shampoo). In some embodiments, the invention providessunscreen compositions (“sunscreen additives”) that may be added to abodywash preparation to impart sun protection. In some embodiments, theinvention provides a combination of a sunscreen additive and a bodywashpreparation (“sunscreen/bodywash”). Thus, a sunscreen additive of theinvention may be mixed with a conventional bodywash; alternatively, theinvention provides pre-mixed sunscreen/bodywash. In either case, thesunscreen/bodywash composition is generally applied in the same manneras the bodywash alone and, typically, rinsed, with additive, e.g.,sunscreen protection, being left on the skin after rinsing. In somecases, e.g., soapless cleansers, the bodywash is applied withoutrinsing. For sunscreen additives as part of a sunscreen/bodywash, thesunscreen protection after application and, typically, rinsing is, onaverage, greater than an SPF of 1, up to about SPF 50. As used herein inthe context of SPF, “average SPF” is the SPF, determined as describedherein, for about 5 to about 50 subjects, or about 5 to about 20subjects, or about 5 to about 10 subjects, where the subjects preferablyhave Type II skin. In some embodiments, the average SPF provided by thesunscreen/bodywash after rinsing is about 1 to about 50, or about 2 toabout 50, or about 2 to about 40, or about 2 to about 30, or about 2 toabout 20, or about 2 to about 10, or about 2 to about 5, or about 5 toabout 25, or about 5 to about 20, or about 5 to about 15, or about 5 toabout 10. In some embodiments, the average SPF provided by thesunscreen/bodywash, after rinsing, is above about 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some preferredembodiments, the average SPF after rinsing is above about 2. In somepreferred embodiments, the average SPF after rinsing is above about 5.In some preferred embodiments, the average SPF after rinsing is aboveabout 10. In some preferred embodiments, the average SPF after rinsingis above about 15. In some embodiments, the average SPF provided by thesunscreen/bodywash of the invention remains above about 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, for anaverage of at least about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or morethan about 10 hours after rinsing. In some embodiments the average SPFprovided by the sunscreen/bodywash of the invention increases with eachadditional washing after a first wash, so that after a second, third,fourth, or fifth wash, the SPF provided can be above about 2, 4, 6, 8,10, 15, 20, 25, 30, 40, 45, or more than about 45.

SPF is a commonly used measure of photo protection of a sunscreenagainst erythema. This number is derived from another parameter, theminimal erythemal dose (MED). MED is defined as the “least exposure doseat a specified wavelength that will elicit a delayed erythema response.”The MED indicates the amount of energy irradiating the skin and theresponsiveness of the skin to the radiation. The SPF of a particularphoto protector is obtained by dividing the MED of protected skin by theMED of unprotected skin. The higher the SPF, the more effective theagent in preventing sunburn. The SPF value tells how many times longer aperson can stay in the sun before the person will experience 1 MED. Forexample, utilizing a sunscreen with an SPF of 6 will allow an individualto stay in the sun six times longer before receiving 1 MED. As the SPFvalue of a sunscreen increases, the less chance exists for developmentof tanning of the skin. Typically, commercially available sunscreeningproducts have SPF values ranging from about 2 to 45.

Methods for measuring SPF are described in, e.g., FDA monograph C.F.R.21. A method for applying the sunscreen prior to measurement is asfollows: Wet 50 cm² square area of testing site with 10 ml of waterdelivered with a syringe. Apply test sample as per FDA monograph toarea. Work lather on the subject for 3 minutes to allow the product toabsorb into the skin. Rinse area after 2 additional minutes with 20 mlof water. Pat dry and allow 15 minutes before exposure to radiation asper FDA monograph.

In some embodiments, after application of the bodywash containing theadditive (e.g., sunscreen) to the skin followed by rinsing, the additive(e.g., sunscreen) penetrates to an average of at least about 5 micronsbeneath the skin surface. In some embodiments, the additive penetratesto an average of at least about 10, 15, 20, 25, 30, 40, 50, 60, 70, 80,90, 100, 120, or 150 microns beneath the skin surface. In someembodiments, after application of the bodywash containing the additive(e.g., sunscreen) to the skin followed by rinsing, the additive (e.g.,sunscreen) penetrates to an average of no more than about 30 micronsbeneath the skin surface. In some embodiments, the additive penetratesto an average of no more than about 50, 40, 30, 25, 20, 15, 10, or 5microns beneath the skin surface. In some embodiments, after applicationof the bodywash containing the additive (e.g., sunscreen) to the skinfollowed by rinsing, the additive (e.g., sunscreen) penetrates to anaverage of about 5 to about 50, or about 5 to about 40, or about 5 toabout 30, or about 10 to about 40, or about 15 to about 40, or about 20to about 40, or about 5, 10, 15, 20, 25, 30, 25, 40, 45, or 50 micronsbeneath the skin surface. Depth of penetration may be tested by tapestripping methods, as are well-known in the art.

The sunscreen additives and sunscreen/bodywashes of the inventioncontain at least one sunscreen. In some embodiments, the sunscreenadditives of the invention contain one, two, three, four, or more thanfour sunscreens. In preferred embodiments, the sunscreen additives ofthe invention include three sunscreens. In other preferred embodiments,the sunscreen additives of the invention include four sunscreens. Thesunscreens may be organic or inorganic. The sunscreens may be a UVAabsorber, a UVB absorber, a physical blocker, or any combinationthereof. In some embodiments one or more of the sunscreens isencapsulated. A number of types of encapsulation may be employed asdescribed herein.

Compositions of the invention may include one or more actives that arenot sunscreens, where the composition is designed to be an additive to abodywash. In some compositions of the invention, the actives areprovided in combination with one or more sunscreens. In somecompositions, the actives are provided without sunscreen.

The additives, e.g., sunscreen additives, and additive/bodywashes, e.g.,sunscreen/bodywashes, of the invention may further include one or morecomponents to provide a positive charge to the system to assist withattachment to protein and other charged components of skin and/or hair,e.g., cationic polymeric agents. The cationic polymer may be, forexample, a quaternium, e.g., polyquaternium.

The additives, e.g., sunscreen additives, and additive/bodywashes, e.g.,sunscreen/bodywashes, of the invention may further include a filmformer.

Other optional ingredients of the additives, e.g., sunscreen additives,and additive/bodywashes, e.g., sunscreen/bodywashes, of the inventioninclude preservatives, antioxidants, chelating agents, liquidhydrocarbon (e.g., similar to pentane), foaming agents (e.g., a cationicfoaming agent), skin nourishing components, antibacterials, medicinals,and the like, as described below.

The additives, e.g., sunscreen additives, of the invention may becombined with any conventional bodywash. The bodywash composition withwhich the additive, e.g., sunscreen additive is combined may be anybodywash known in the art or apparent to one of skill in the art, asdescribed above. In embodiments where the additive is a non-sunscreenactive, the additive may be combined with any composition intended fortopical application. In these embodiments, the additive is oftenencapsulated, e.g., in sol-gel microcapsules.

In some embodiments the invention provides an additive, e.g., sunscreenadditive, in combination with a bodywash composition to provide anadditive/bodywash, e.g. sunscreen/bodywash, composition. In theseembodiments, the additive, e.g., sunscreen additives, of the inventionare provided in combination with one or more surfactants. Thesurfactant(s) may be cationic, anionic, nonionic, zwitterionic,amphoteric, or any combination thereof. In preferred embodiments, thesunscreen/bodywash compositions of the invention include at least onecationic surfactant.

A. Sunscreens

The sunscreen additives and sunscreen/bodywashes of the inventioncontain at least one sunscreen. The sunscreen may be organic orinorganic, or a combination of both may be used. Sunscreens of use inthe invention include UV absorbers or blockers (e.g., many inorganicsunscreens are UV blockers). UV absorbers may be a UVB or UVA absorber(e.g., UVA I or UVA II absorber). In some embodiments, the sunscreenadditives or sunscreen/bodywashes of the invention include an organicand an inorganic sunscreen. In some embodiments, the sunscreen additivesor sunscreen/bodywashes of the invention include more than one organicsunscreen (e.g., at least one UVB absorber and at least one UVAabsorber) and at least one inorganic sunscreen. In some embodiments, thesunscreen additives of the invention include only a physical blockersunscreen, e.g., titanium dioxide. These embodiments may further containa cationic polymer and/or a film former, as well as any other componentsdescribed herein for sunscreen additives.

Additional ingredients may include film formers, cationic polymers,antioxidants, preservatives, and the like, as described herein. In someembodiments, the sunscreen additives or sunscreen/bodywashes of theinvention include an organic and an inorganic sunscreen. In someembodiments, the sunscreen additives or sunscreen/bodywashes of theinvention include more than one organic sunscreen (e.g., at least oneUVB absorber and at least one UVA absorber) and at least one inorganicsunscreen.

In preferred embodiments, one or more of the sunscreens used in theinvention are encapsulated.

Any sunscreen known in the art or apparent to the skilled artisan may beused in the invention. The term “sunscreen” or “sunscreen agent” as usedherein defines ultraviolet ray-blocking compounds exhibiting absorptionor blockage within the wavelength region between about 290 and 420 nm.Sunscreens may be classified into five groups based upon their chemicalstructure: para-amino benzoates; salicylates; cinnamates; benzophenones;and miscellaneous chemicals including menthyl anthralinate and digalloyltrioleate. Inorganic sunscreens may also be used including titaniumdioxide, zinc oxide, iron oxide and polymer particles such as those ofpolyethylene and polyamides.

Specific suitable sunscreens include, for example: p-aminobenzoic acid,its salts and its derivatives (ethyl, isobutyl, glyceryl esters;p-dimethylaminobenzoic acid); Anthranilates (i.e., o-aminobenzoates;methyl, menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, andcyclohexenyl esters); Salicylates (amyl, phenyl, benzyl, menthyl,glyceryl, and dipropylene glycol esters); Cinnamic acid derivatives(methyl and benzyl esters, alpha-phenyl cinnamonitrile; butyl cinnamoylpyruvate); Dihydroxycinnamic acid derivatives (umbelliferone,methylumbelliferone, methylaceto-umbelliferone); Trihydroxycinnamic acidderivatives (esculetin, methylesculetin, daphnetin, and the glucosides,esculin and daphnin); Hydrocarbons (diphenylbutadiene, stilbene);Dibenzalacetone and benzalacetophenone; Naphtholsulfonates (sodium saltsof 2-naphthol-3,3-disulfonic and of 2-naphthol-6,8-disulfonic acids);Dihydroxynaphthoic acid and its salts; o- andp-Hydroxybiphenyldisulfonates; Coumarin derivatives (7-hydroxy,7-methyl, 3-phenlyll); Diazoles (2-acetyl-3-bromoindazole, phenylbenzoxazole, methyl naphthoxalole, various aryl benzothiazoles); Quininesalts (bisulfate, sulfate, chloride, oleate, and tannate); quinolinederivatives (8-hydroxyquinoline salts, 2-phenylquinoline); Hydroxy- ormethoxy substituted benzophenones; Uric and vilouric acids; Tannic acidand its derivatives (e.g., hexaethylether); (Butyl carbityl) (6-propylpiperonyl) ether; Hydroquinone; Benzophenones (Oxybenzene,Sulisobenzone, Dioxybenzone, Benzoresorcinol,2,2′,4,4′-Tetrahydroxybenzophenone,2,2′-Dihydroxy-4,4′-dimethoxybenzophenone, Octabenzone;4-Isopropyhldibenzoylmethane; Butylmethoxydibenzoylmethane; Etocrylene;and 4-isopropyl-di-benzoylmethane; titanium dioxide, iron oxide, zincoxide, and mixtures thereof. Other cosmetically-acceptable sunscreensand concentrations (percent by weight of the total cosmetic sunscreencomposition) include diethanolamine methoxycinnamate (10% or less),ethyl-[bis(hydroxypropyl)]aminobenzoate (5% or less), glycerylaminobenzoate (3% or less), 4-isopropyl dibenzoylmethane (5% or less),4-methylbenzylidene camphor (6% or less), terephthalylidene dicamphorsulfonic acid (10% or less), and sulisobenzone (also calledbenzophenone-4, 10% or less).

In preferred embodiments, sunscreens are FDA-approved or approved foruse in the European Union. For example, FDA-approved sunscreens may beused, singly or, preferably, in combination. See, e.g., U.S. Pat. Nos.5,169,624; 5,543,136; 5,849,273; 5,904,917; 6,224,852; 6,217,852; andSegarin et al., chapter Vil, pages 189 of Cosmetics Science andTechnology, and Final Over-the-Counter Drug Products Monograph onSunscreens (Federal Register, 1999:64:27666-27963), all of which areincorporated herein by reference.

For example, for a product marketed in the United States, preferredcosmetically-acceptable sunscreens and concentrations (reported as apercentage by weight of the total cosmetic sunscreen composition, andreferring to the final percentage of the sunscreen after addition to thebodywash) include: aminobenzoic acid (also called para-aminobenzoic acidand PABA; 15% or less; a UVB absorbing organic sunscreen), avobenzone(also called butyl methoxy dibenzoylmethane; 3% or less, a UVA Iabsorbing organic sunscreen), cinoxate (also called 2-ethoxyethylp-methoxycinnamate; 3% or less, a UVB absorbing organic sunscreen),dioxybenzone (also called benzophenone-8; 3% or less, a UVB and UVA IIabsorbing organic sunscreen), homosalate (15% or less, a UVB absorbingorganic sunscreen), menthyl anthranilate (also called menthyl2-aminobenzoate; 5% or less, a UVA II absorbing organic sunscreen),octocrylene (also called 2-ethylhexyl-2-cyano-3,3 diphenylacrylate; 10%or less, a UVB absorbing organic sunscreen), octyl methoxycinnamate(7.5% or less, a UVB absorbing organic sunscreen), octyl salicylate(also called 2-ethylhexyl salicylate; 5% or less, a UVB absorbingorganic sunscreen), oxybenzone (also called benzophenone-3; 6% or less,a UVB and UVA II absorbing organic sunscreen), padimate O (also calledoctyl dimethyl PABA; 8% or less, a UVB absorbing organic sunscreen),phenylbenzimidazole sulfonic acid (water soluble; 4% or less, a UVBabsorbing organic sunscreen), sulisobenzone (also called benzophenone-4;10% or less, a UVB and UVA II absorbing organic sunscreen), titaniumdioxide (25% or less, an inorganic physical blocker of UVA and UVB),trolamine salicylate (also called triethanolamine salicylate; 12% orless, a UVB absorbing organic sunscreen), and zinc oxide (25% or less,an inorganic physical blocker of UVA and UVB).

For a product marketed in the European Union, preferredcosmetically-acceptable photoactive compounds and concentrations(reported as a percentage by weight of the total cosmetic sunscreencomposition, and referring to the final percentage of the sunscreenafter addition to the bodywash) include: PABA (5% or less), camphorbenzalkonium methosulfate (6% or less), homosalate (10% or less),benzophenone-3 (10% or less), phenylbenzimidazole sulfonic acid (8% orless, expressed as acid), terephthalidene dicamphor sulfonic acid (10%or less, expressed as acid), butyl methoxydibenzoylmethane (5% or less),benzylidene camphor sulfonic acid (6% or less, expressed as acid),octocrylene (10% or less, expressed as acid), polyacrylamidomethylbenzylidene camphor (6% or less), octyl methoxycinnamate (10% or less),PEG-25 PABA (10% or less), isoamyl p-methoxycinnamate (10% or less),ethylhexyl triazone (5% or less), drometrizole trielloxane (15% orless), diethylhexyl butamido triazone (10% or less), 4-methylbenzylidenecamphor (4% or less), 3-benzylidene camphor (2% or less), ethylhexylsalicylate (5% or less), ethylhexyl dimethyl PABA (8% or less),benzophenone-4 (5%, expressed as acid), methylene bis-benztriazolyltetramethylbutylphenol (10% or less), disodium phenyl dibenzimidazoletetrasulfonate (10% or less, expressed as acid), bis-ethylhexyloxyphenolmethoxyphenol triazine (10% or less), methylene bisbenzotriazolyltetramethylbutylphenol (10% or less, also called TINOSORB M), andbisethylhexyloxyphenol methoxyphenyl triazine (10% or less, also calledTINOSORB S).

In some embodiments, the sunscreen additives or sunscreen/bodywashes ofthe invention include a silicone long-chain molecule with chromophores,e.g., PARASOL SLX (DSM Nutritional Products), which contains benzylmalonate chromophores attached to specific points on a polysiloxanechain. Thus, in some embodiments, the invention provides a sunscreenadditive or sunscreen/bodywash composition that contains sunscreen thatcomprises a silicone long-chain molecule with chromophores. For example,compositions of the invention include a composition containing octylmethoxycinnamate, octocrylene, avobenzone, titanium dioxide, and asilicone long-chain molecule with chromophores. The silicon long-chainmolecule may be used in sunscreen additives at about 0.5 to about 5%, orin sunscreen/bodywashes at about 0.2 to about 2%.

Inorganic physical blockers of UVA and UVB useful in the inventionfurther include iron oxide and polymer particles such as those ofpolyethylene and polyamides.

In some embodiments, the sunscreen additives and sunscreen/bodywashescontain at least one sunscreen active that is cinnamate (e.g.,Octylmethoxycinnamate (ethyl hexyl methoxycinnamate), (available underthe tradename PARSOL MCX), oxybenzone (e.g., benzophenone-3(2-Hydroxy-4-Methoxybenzophenone), avobenzone(4-tert-Butyl-4′-methoxydibenzoylmethane or PARSOL 1789), octylsalicylate (2-Ethylhexyl Salicylate), octocrylene (2-Ethylhexyl2-Cyano-3,3-Diphenylacrylate), methyl anthranilate, and/or titaniumdioxide, or combinations thereof.

Sunscreen additives and sunscreen/bodywashes of the invention may, insome embodiments, contain as a sunscreen component only titaniumdioxide. When titanium dioxide is used in compositions of the invention,either alone or in combination with other sunscreens, the titaniumdioxide can have an anatase, rutile, or amorphous structure. Thetitanium dioxide particles can be uncoated or can be coated with avariety of materials including, but not limited to, aluminum compoundssuch as aluminum oxide, aluminum stearate, aluminum laurate and thelike; phospholipids such as lecithin; silicone compounds; and mixturesthereof. Various grades and forms of titanium dioxide are described inCTFA Cosmetic Ingredient Dictionary, Third Edition (1982), pp. 318–319;U.S. Pat. No. 4,820,508 to Wortzman, issued Apr. 11, 1989; and WorldPatent No. WO 90/11067 to Elsom et al, published Oct. 4, 1990; thesethree references are incorporated by reference herein in their entirety.Suitable grades of titanium dioxide for use in the compositions of thepresent invention are available commercially such as the MT micronizedseries from Tri-K Industries (Emerson, N.J.). These micronized titaniumdioxides generally have a mean primary particle size ranging from about10 nm to about 50 nm. For example, titanium dioxide having a meanprimary particle size of about 15 mm is available under the tradedesignations MT-15OW (uncoated) and MT-100T (coated with stearic acidand aluminum compounds). Uncoated titanium dioxides having mean primaryparticle sizes of around 35 nm and around 50 nm are available under thetrade designations MT-500B and MT-600B, respectively. Other coatedtitanium dioxides having a mean primary particle size around 15 nminclude MT-100F (modified with stearic acid and iron hydroxide) andMT-100S (treated with lauric acid and aluminum hydroxide). Mixtures oftwo or more types and particle size variations of titanium dioxide canbe used in the present invention.

A particularly preferred form of titanium dioxide is silica-coated TiO₂.Such a silica-coated TiO₂ is available under the tradename T-AVO(Eusolex).

If a zinc compound is chosen as the inorganic sunscreen, some zinc-basedcompositions (e.g., Z-Cote™ HP1 [registered trademark, SkinCeuticals])provide micro-fine zinc oxide coated with a form of dimethicone. Asexpressed by the manufacturer, the dimethicone coating transforms thefrequently granular and pasty particles of zinc oxide to a smoothformulation which is transparent. The micronizing of these particlesachieves the important advantage of providing effective sunscreeningwithout giving the appearance of skin coated with white paint.

Also to be noted in relation to inorganic blockers are Tioveil andSpectraveil (both of the Tioxide Group). Tioveil include products whichare 40% dispersions of surface-treated titanium dioxide in a range ofcosmetic vehicles. Spectraveil include products which are 60%dispersions of zinc oxide in a range of cosmetic vehicles. In certainvariations, these products may be film-formers and may have advantageoususes here.

In sunscreen additives, the total sunscreens comprise about 0.1–50%, orabout 1–30%, or about 1–25%, or about 3–25%, or about 5–25%, or about10–25% or about 15–25%, or about 5, 10, 15, 20, 25, 30, 35, 40, 45, or50% of the composition (all percentages herein are weight percent unlessotherwise specified). In sunscreen/bodywash compositions, the totalsunscreens can comprise 0.05–30%, or about 0.5–15%, or about 0.5–12%, orabout 1.5–12%, or about 2.5–12%, or about 5–12% or about 7–12%, or about2.5, 5, 7.5, 10, 12.5, 15, 20, 25, 30, 33, 35, 40, 45, 50, or more than50% of the composition.

In some embodiments, a sunscreen additive of the invention includesoctyl methoxycinnamate at about 4.5–9%, Octocrylene at about 0.5–15%,Avobenzone (e.g., PARSOL 1789) at about 2–4%, and titanium dioxide atabout 3–9%. In some embodiments, the octyl methoxy cinnamate isencapsulated, e.g., in amorphous silica. Such encapsulated octyl methoxycinnamate is commercially available under the trade name UV PEARLS;about 20–40% UV PEARLS supplies about 4.5–9% octyl methoxy cinnamate. Insome embodiments, a sunscreen additive of the invention includes octylmethoxycinnamate at about 7.6% (in some embodiments, encapsulated asdescribed, e.g., in UV PEARLS wherein the UV PEARLS are provided atabout 33.3%), Octocrylene at about 11.3%, Avobenzone (PARSOL 1789) atabout 2.8%, and titanium dioxide at about 6.4%. The sunscreen additivesmay further include a polyquaternium, e.g., polyquaternium-4. In someembodiments, the polyquaternium-4 is present at about 0.5% to about 5%,in some embodiments, the polyquaternium-4 is present at about 2.8%. Thesunscreen additives may further include a film-former, which maycomprise dimethicone and/or petrolatum, and/or a preservative, such asBHT. This sunscreen additive may be added to a conventional bodywashformulation (e.g., SUAVE Bodywash) in a ratio of about one partsunscreen additive to two parts bodywash (w/w). Other ratios areencompassed by the invention, e.g., about one part sunscreen additive toabout 0.2, 0.5, 0.7 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.2, 3.5, 3.7,4.0, 4.2, 4.5, 4.7, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 12, 15, or 20 partsbodywash (w/w).

It will be appreciated by those of skill in the art that the variousingredients of the sunscreen additive may be added to the bodywash allat once, or in groups, or separately. In some embodiments, the sunscreenadditive comprises at least two components. For example, the firstcomponent may comprise all the ingredients except an inorganic orphysical blocker sunscreen, and the second component may comprise theinorganic or physical blocker sunscreen. The first component is added tothe bodywash with thorough mixing, then the second component is added.For example, in some embodiments, all ingredients except the titaniumdioxide are mixed, then added to the bodywash, and then the titaniumdioxide is added (see Examples).

In some embodiments, the sunscreen additives of the invention includeabout 0.1 to 7.5 weight percent of octylmethoxy cinnamate, about 0.1 to6 parts weight percent of octyl salicylate, about 0.1 to 5 parts weightpercent of oxybenzone, about 1 to 10 weight percent of cationicsurfactant, and about 0.01 to 1 weight percent of a quaternizedcompound. These composition may further include a film former. Thesecompositions may further include 0.01 to 1 weight percent of apreservative.

Encapsulation Sunscreens and other actives used in the invention may beencapsulated. One or more of the sunscreens used in a composition may beencapsulated; preferably, all sunscreens used are encapsulated.Sunscreen actives may be encapsulated together, or may be encapsulatedseparately, in any combination, in the same or in different types ofencapsulations. Generally, encapsulation involves trapping the sunscreenin, e.g., a vesicle. Depending on the vesicle of choice, the vesicle maybreak open when applied. Without being limited by theory, it is thoughtthat the vesicle breaks open in various types of encapsulation due tofriction, temperature, or pH from the skin or hair, or some combinationof these. By choosing the appropriate capsule and additives for thesystem, the stability, durability, and/or SPF provided by the sunscreenadditives and sunscreen/bodywashes of the invention can be increased.

Any means of encapsulation known in the art, including but not limitedto liposomes, maltodextrin capsules, silica gels, siloxanes, and thelike, may be used in the compositions of the invention. A cationic orcatanionic in dry powder form may also be used to encapsulate sunscreen.Commercial embodiments of encapsulated sunscreens or vehicles suitablefor encapsulating sunscreens include CATEZOMES (Engelhard Corp.),EUSOLEX UV PEARLS (EMD Biosciences), and others known in the art.Methods of encapsulation suitable for delivering benefit agents that aremixed with a bodywash composition are well-known in the art. See, e.g.,U.S. Pat. Nos. 6,825,161; 6,436,375; 6,238,650; 6,468,509, 6,362,146;6,074,630; 5,455,048; 5,770,556; 5,955,409; 5,876,755; 4,803,195;5,508,259; 4,749,501; 6,248,703; 5,476,660; and 4,904,524 and EP Pat.Nos. 0,254,447; 0,025,379; and 0,399,911.

A particularly preferred method of encapsulation is sol-gelencapsulation. This technique is described in, e.g., U.S. Pat. Nos.6,238,650; 6,436,375, 6,303,149; and 6,468,509. Any or all of thesunscreens and/or other active ingredients of the compositions of theinvention may be encapsulated by such sol-gel encapsulation. The sol-gelcapsules may be prepared so as to have a surface charge, e.g., acationic charge. This is advantageous in that otherwise water-insolublecomponents may be encapsulated within the microcapsules, which are thenfreely miscible in water, e.g., without the need for an emulsifyingagent. For example, in some embodiments, a UVA absorber, a UVB absorber(e.g., octyl methoxycinnamate) and/or a physical blocker, e.g., titaniumdioxide, is provided as a silica sol-gel encapsulate, optionally withfurther ingredients including PVP, Chlorphenesin, and an antioxidantsuch as BHT. A commercial embodiment of such an encapsulation containingoctyl methoxycinnamate, PVP, chlorphenesin, and BHT, is available underthe trade name EUSOLEX UV PEARLS (EMD Biosciences). Such a silicasol-gel encapsulated UVB absorber, e.g., octyl methoxycinnamate, may beused in a sunscreen additive at a concentration that results in a finalconcentration of the UVB absorber of about 1% to about 40%, or about 2%to about 20%, or about 2% to about 10%, or about 5% to about 10%, orabout 6%, 7%, 7.4%, 7.5%, 7.6%, 8%, or 9%. The preferred finalconcentration is about 7.6%. In other embodiments, more than onesunscreen is encapsulated as silica sol-gel encapsulate. In theseembodiments, the final concentration of each of the sunscreens,independently, in the final sunscreen additive, is about 1% to about40%, or about 2% to about 20%, or about 2% to about 10%, or about 1%,2%, 3%, 4%, 5%, 6%, 7%, 7.5%, 8%, 9%, or 10%. The sunscreens may beencapsulated together or separately, or any combination thereof. In someembodiments, the invention provides an additive for addition to abodywash that includes a sunscreen encapsulated in a sol-gelmicrocapsule and a cationic polymer (described below). Furtheringredients in these embodiments may include a film former, antioxidant,preservative, chelating agent, thickener, emollient, and/or other activeand inactive ingredients as described herein.

In some embodiments wherein encapsulation, e.g., sol-gelmicroencapsulation, is utilized, the composition of the microcapsule,e.g., sol-gel microcapsule, may be varied so as to allow for varyingamounts of the active, e.g., sunscreen, within the microcapsule to bereleased. The microcapsules, e.g., sol-gel microcapsules, can beprepared so as to experience no or minimal breakage when applied to theskin and when left on the skin. Alternatively, the microcapsules, e.g.,sol-gel microcapsules, can be prepared so as to experience variousdegrees of breakage, on average, when applied to the skin and when lefton the skin. Thus, the microcapsules, e.g., sol-gel microcapsules, maybe prepared so as to experience about 0% breakage, or breakage in arange from about 0.1, 0.5, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, or90% to about 0.5, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90%, afterapplication (or application and rinsing in the case of a or bodywashcontaining the microcapsules). Furthermore, the microcapsules may beformulated so as to break open in response to conditions that occur onthe skin, so that after application the microcapsules act to releasetheir contents in a time-release or controlled manner. Non-limitingexemplary skin or hair conditions that can vary with the user'senvironment, the variation of which can trigger breakage ofmicrocapsules, include pH, temperature, friction, exposure to light orair, pressure, and the like.

Other forms of immobilization or entrapment of sunscreen and otheractive components are also useful. For example, as a further variant ofthe use of chemical sunscreen agents, compositions of the invention mayemploy an organic sunscreen such as octyl methoxycinnamate trappedwithin a matrix. A commercial example of such a composition is found inSunCaps™) (trademark, SkinCeuticals) in which the organic sunscreenmolecules are evenly distributed throughout the particle.

B. Non-sunscreen Actives

In one aspect, the invention provides additives containing non-sunscreenactive ingredients, where the additive is designed to be added to acomposition for topical application, e.g., a bodywash. These actives maybe used in combination with the sunscreens described above in asunscreen additive or sunscreen/bodywash, or may be used in separate,non-sunscreen compositions. In some embodiments, at least one of theactives is encapsulated. In another aspect, the invention provides acomposition for topical application, e.g., a bodywash, containing one ormore such actives. These actives may be used in combination with thesunscreens described above in a sunscreen additive orsunscreen/bodywash, or may be used in separate, non-sunscreencompositions.

Non-limiting examples of non-sunscreen actives useful in compositions ofthe invention include sunless tanning actives, skin lightening actives,anti-acne actives, anti-skin wrinkling and anti-skin aging actives,vitamins, anti-inflammatory actives, anesthetic actives, analgesicactives, anti-pruritic actives, anti-microbial actives (e.g.antifungals, antibacterials, and antiparasitics), anti-virals,anti-allergenics, medicinal actives (e.g., skin rash, skin disease anddermatitis medications), anti-cellulite additives, insect repellantactives, antioxidants, hair growth promoters, hair growth inhibitors,hair bleaching agents, deodorant compounds, and mixtures andcombinations thereof.

Sunless tanning actives include dihydroxyacetone (DHA); glycerylaldehyde; tyrosine and tyrosine derivatives such as malyltyrosine,tyrosine glucosinate, and ethyl tyrosine; phospho-DOPA, indoles andderivatives; and mixtures thereof.

Non-limiting examples of skin lightening actives include EMBLICA (alsoan antioxidant), monobenzone (a depigmenting agent), kojic acid,arbutin, ascorbic acid and derivatives thereof (e.g., magnesium ascorbylphosphate or sodium ascorbyl phosphate), and extracts (e.g., mulberryextract, placental extract). Non-limiting examples of skin lighteningagents suitable for use herein also include those described in WO95/34280, WO 95/07432, and WO 95/23780.

Vitamins may be included in the compositions of the present invention.Examples include Vitamin A and derivatives thereof (including, forexample, retinol, see anti-wrinkling actives), ascorbic acid (Vitamin Cand derivatives), Vitamin B (e.g., riboflavin, vitamin B₂), biotin,Vitamin D (all forms), Vitamin E and derivatives thereof such astocopheryl acetate, beta-carotene, panthothenic acid and mixturesthereof.

Anti-acne actives include benzoyl peroxide, erythromycin, clindamycinphosphate, 5,7-dichloro-8-hydroxyquinoline, resorcinol, resorcinolacetate, salicylic acid, azaleic acid, long chain dicarboxylic acids,sulfur, zinc, various natural agents such as those derived from greentree, and mixtures thereof. Other non-limiting examples of suitableanti-acne actives for use herein are described in U.S. Pat. No.5,607,980, which description is incorporated herein by reference.

Anti-skin wrinkling actives include a variety of agents, often incombination, that prevent or treat wrinkling through a variety ofactions. Many approaches are taken to reduce the appearance of facialwrinkles based on the understanding of the molecular basis of wrinkleformation. Such treatments include cosmetic products, drug therapy andsurgical procedures. For example, many cosmetic products contain hydroxyacids, which may stimulate collagen synthesis. Another common treatmentutilizes retinol, retinoic, retinol palmitate, a derivative of vitaminA, (or its stronger, prescribed version Retin-A and Renova) which helpscollagen production. Bicyclic aromatic compounds with retinoid-typeactivity, which are useful in particular in preventing or treatingvarious keratinization disorders, are described in EP 679 630. Thesecompounds are particularly active for repairing or combatingchronological or actinic ageing of the skin, for example such as inanti-wrinkle products. Antioxidants such as vitamin C and E and coenzymeQ-10 are believed to counteract free radicals, which damage cells andcause aging and have been used in treatments of wrinkles. Recently, theFDA approved cosmetic use of Botox (an extremely diluted form ofbotulinum toxin) to treat glabella frown lines. Thus non-sunscreenactives of the invention that are anti-skin aging or anti-wrinklingactives may contain, alone or in combination, the bicyclic aromaticcompounds defined above, other compounds which have retinoid-typeactivity, free-radical scavengers, hydroxy or keto acids or derivativesthereof. The term “free-radical scavenger” refers to, for example,α-tocopherol, superoxide dismutase, ubiquinol or certain metal-chelatingagents. Hydroxy acids include, e.g., alpha-hydroxy acids such as lacticacid and glycolic acid or beta-hydroxy acids such as salicylic acid andsalicylic acid derivatives such as the octanoyl derivative; otherhydroxy acids and keto acids include malic, citric, mandelic, tartaricor glyceric acids or the salts, amides or esters thereof.

Other anti-wrinkling agents and anti-skin aging agents useful in theinvention include sulfur-containing D and L amino acids and theirderivatives and salts, particularly the N-acetyl derivatives, apreferred example of which is N-acetyl-L-cysteine; thiols, e.g. ethanethiol; fat-soluble vitamins, ascorbyl palmitate, ceramides,pseudoceramides (e.g., pseudoceramides described in U.S. Pat. Nos.5,198,210; 4,778,823; 4,985,547; 5,175,321, all of which areincorporated by reference herein), phospholipids (e.g., distearoyllecithin phospholipid), fatty acids, fatty alcohols, cholesterol, plantsterols, phytic acid, lipoic acid; lysophosphatidic acid, and skin peelagents (e.g., phenol and the like), and mixtures thereof. Preferredfatty acids or alcohols are those that have straight or branched alkylchains containing 12–20 carbon atoms. A particularly preferred fattyacid is linoleic acid since linoleic acid assists in the absorption ofultraviolet light and furthermore is a vital component of the naturalskin lipids. Other non-limiting examples of suitable anti-wrinkleactives for use herein are described in U.S. Pat. No. 6,217,888, whichdescription is incorporated herein by reference.

Anti-inflammatory actives include steroidal, non-steroidal, and othercompounds.

Non-limiting examples of steroidal anti-inflammatory agents suitable foruse herein include corticosteroids such as hydrocortisone,hydroxyltriamcinolone, alpha-methyl dexamethasone,dexamethasone-phosphate, beclomethasone dipropionates, clobetasolvalerate, desonide, desoxymethasone, desoxycorticosterone acetate,dexamethasone, dichlorisone, diflorasone diacetate, diflucortolonevalerate, fluadrenolone, fluclorolone acetonide, fludrocortisone,flumethasone pivalate, fluosinolone acetonide, fluocinonide, flucortinebutylesters, fluocortolone, fluprednidene (fluprednylidene) acetate,flurandrenolone, halcinonide, hydrocortisone acetate, hydrocortisonebutyrate, methylprednisolone, triamcinolone acetonide, cortisone,cortodoxone, flucetonide, fludrocortisone, difluorosone diacetate,fluradrenolone, fludrocortisone, diflurosone diacetate, fluradrenoloneacetonide, medrysone, amcinafel, amcinafide, betamethasone and thebalance of its esters, chloroprednisone, chlorprednisone acetate,clocortelone, clescinolone, dichlorisone, diflurprednate, flucloronide,flunisolide, fluoromethalone, fluperolone, fluprednisolone,hydrocortisone valerate, hydrocortisone cyclopentylpropionate,hydrocortamate, meprednisone, paramethasone, prednisolone, prednisone,beclomethasone dipropionate, triamcinolone, and mixtures thereof may beused. The preferred steroidal anti-inflammatory for use ishydrocortisone.

Nonsteroidal anti-inflammatory agents are also suitable for use hereinas skin active agents in the compositions of the invention. Non-limitingexamples of non-steroidal anti-inflammatory agents suitable for useherein include oxicams (e.g., piroxicam, isoxicam, tenoxicam, sudoxicam,CP-14,304); salicylates (e.g., aspirin, disalcid, benorylate, trilisate,safapryn, solprin, diflunisal, fendosal); acetic acid derivatives (e.g.,diclofenac, fenclofenac, indomethacin, sulindac, tolmetin, isoxepac,furofenac, tiopinac, zidometacin, acematacin, fentiazac, zomepirac,clindanac, oxepinac, felbinac, ketorolac); fenamates (e.g., mefenamic,meclofenamic, flufenamic, niflumic, tolfenamic acids); propionic acidderivatives (e,g., ibuprofen, naproxen, benoxaprofen, flurbiprofen,ketoprofen, fenoprofen, fenbufen, indopropfen, pirprofen, carprofen,oxaprozin, pranoprofen, miroprofen, tioxaprofen, suprofen, alminoprofen,tiaprofenic); pyrazoles (e.g., phenylbutazone, oxyphenbutazone,feprazone, azapropazone, trimethazone); and combinations thereof as wellas any dermatologically acceptable salts or esters of thereof. COX-2inhibitors are also suitable for use herein, and include, but are notlimited to, AZD 3582 (ASTRAZENECA and NicOx), Celecoxib (PHARMACIACorp.)(4-[5-(4-methylphenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl]benzenesulfonamide),Meloxicam (BOEHRINGER INGELHEIM Pharmaceuticals)(4-hydroxy-2-methyl-N-(5-methyl-2-thiazolyl)-2H-1,2GW-406381(GLAXOSMITHKLINE), Etoricoxib (MERCK & Co.), Rofecoxib (MERCK & Co.)(4-[4-(methylsulfonyl) phenyl]-3-phenyl-2(5H)-furanone), Lumiracoxib(NOVARTIS Pharma AG), Valdecoxib (PHARMACIA Corp.)(4-(5-methyl-3-phenyl-4-isox-azolyl) benzenesulfonamide), and Etodolac(WYETH Ayerst Laboratories) ((.+−.)1,8-diethyl-1,3,4,9-tetrahydropyrano-[3,4-b]acid).

Other non-limiting examples of suitable anti-inflammatory or similarother skin active agents include candelilla wax, bisabolol (e.g., alphabisabolol), aloe vera, plant sterols (e.g., phytosterol), Manjistha(extracted from plants in the genus Rubia, particularly RubiaCordifolia), and Guggal (extracted from plants in the genus Commiphora,particularly Commiphora Mukul), kola extract, chamomile, red cloverextract, sea whip extract, anise oil, garlic oil, ginger extract,vasoconstrictors such as phenylephrine hydrochloride, and combinationsthereof.

Further non-limiting examples of suitable anti-inflammatory or similarother skin active agents include compounds of the Licorice (the plantgenus/species Glycyrrhiza glabra) family, including glycyrrhetic acid,glycyrrhizic acid, and derivatives thereof (e.g., salts and esters).Suitable salts of the foregoing compounds include metal and ammoniumsalts. Suitable esters include C₂–C₂₄ saturated or unsaturated esters ofthe acids, preferably C₁₀–C₂₄, more preferably C₁₆–C₂₄. Specificnon-limiting examples of the foregoing include oil soluble licoriceextract, the glycyrrhizic and glycyrrhetic acids themselves,monoammonium glycyrrhizinate, monopotassium glycyrrhizinate, dipotassiumglycyrrhizinate, 1-beta-glycyrrhetic acid, stearyl glycyrrhetinate, and3-stearyloxy-glycyrrhetinic acid, disodium3-succinyloxy-beta-glycyrrhetinate, and combinations thereof.

Anesthetic actives include butamben picrate, lidocaine, xylocalne,benzocaine, bupivacaine, chlorprocaine, dibucaine, etidocaine,mepivacaine, tetracaine, dyclonine, hexylcaine, procaine, cocaine,ketamine, pramoxine, phenol, and pharmaceutically acceptable saltsthereof.

Analgesic actives include dyclonine hydrochloride, aloe vera, fentanyl,capsaicin, and the like.

Anti-pruritic actives include alclometasone dipropionate, betamethasonevalerate, and isopropyl myristate MSD.

Anti-microbial actives include antifungal, antibacterial, and antisepticcompounds. Antifungal compounds include, but are not limited to,compounds such as imidazole antifungals. Specific antifungals includebutocouazole nitrate, miconazole, econazole, ketoconazole, oxiconizole,haloprogin, clotrimazole, and butenafine HCl, naftifine, terbinafine,ciclopirox, and tolnaftate. Antibacterial and antiseptic compoundsinclude phenol-TEA complex, mupirocin, triclosan, chlorocresol,chlorbutol, iodine, clindamycin, CAE (Anjinomoto Co., Inc., containingDL-pyrrolidone Carboxylic acid salt of L-Cocoyl Arginine Ethyl Ester),povidone-iodine, polymyxin b sulfate-bacitracin, zinc-neomycinsulfate-hydrocortisone, chloramphenicol, methylbenzethonium chloride,and erythromycin and antiseptics (e.g., benzalkonium chloride,benzethonium chloride, chlorhexidine gluconate, mafenide acetate,nitrofurazone, nitromersol and the like may be included in compositionsof the invention. Many deodorant compounds are also antimicrobial (seebelow). Antiparasitics, such as lindane may also be included.

Further examples of antimicrobial and antifungal actives useful in thecompositions of the present invention include, but are not limited to,β-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin,tetracycline, amikacin, 2,4,4′-trichloro-2′-hydroxy diphenyl ether,3,4,4′-trichlorocarbanilide, phenoxyethanol, phenoxy propanol,phenoxyisopropanol, doxycycline, capreomycin, chlorhexidine,chlortetracycline, oxytetracycline, ethambutol, hexamidine isethionate,metronidazole, pentamidine, gentamicin, kanamycin, lineomycin,methacycline, methenamine, minocycline, neomycin, netilmicin,paromomycin, streptomycin, tobramycin, miconazole, tetracyclinehydrochloride, erythromycin, zinc erythromycin, erythromycin estolate,erythromycin stearate, amikacin sulfate, doxycycline hydrochloride,capreomycin sulfate, chlorhexidine gluconate, chlorhexidinehydrochloride, chlortetracycline hydrochloride, oxytetracyclinehydrochloride, clindamycin hydrochloride, ethambutol hydrochloride,metronidazole hydrochloride, pentamidine hydrochloride, gentamicinsulfate, kanamycin sulfate, lineomycin hydrochloride, methacyclinehydrochloride, methenamine hippurate, methenamine mandelate, minocyclinehydrochloride, neomycin sulfate, netilmicin sulfate, paromomycinsulfate, streptomycin sulfate, tobramycin sulfate, miconazolehydrochloride, amanfadine hydrochloride, amanfadine sulfate, octopirox,parachlorometa xylenol, nystatin, tolnaftate, zinc pyrithione andclotrimazole

Compositions of the invention may include antiviral agents. Suitableanti-viral agents include, but are not limited to, metal salts (e.g.,silver nitrate, copper sulfate, iron chloride, etc.) and organic acids(e.g., malic acid, salicylic acid, succinic acid, benzoic acid, etc.).In particular compositions which contain additional suitable anti-viralagents include those described in copending U.S. patent applicationsSer. Nos. 09/421,084 (Beerse et al.); Ser. No. 09/421,131 (Biedermann etal.); Ser. No. 09/420,646 (Morgan et al.); and Ser. No. 09/421,179 (Pageet al.), which were each filed on Oct. 19, 1999

Anti-allergenics include antihistamines. Antihistamines can be of H₁ orH₂ antagonists or other types of histamine release inhibitors. The H₁antagonists can be sedating or non-sedating. Examples of H₁-sedatingantihistamines include diphenhydramine (Benadryl), chlorpheniramine,tripelennamine, promethazine, clemastine, doxylamine, benadryl etc.Examples of H₁-non-sedating antihistamines include astemizole,terfenadine, loratadine etc. Examples of H₂ antagonists includecimetadine, famotidine, nizatidine, and ranitidine. Examples ofhistamine-release-inhibitors include cromolyn.

A further active useful in the invention may be a medicinal fortreatment of dermatological conditions such as psoriasis, acne, eczema,and other skin conditions due to disease, pathology, accident, and thelike. Medicinals include burn relief ointments, such aso-amino-p-toluenesulfonamide monoacetate; dermatitis relief agents, suchas the active steroid amcinonide, diflorasone diacetate, andhydrocortisone; diaper rash relief agents, such as methylbenzethoniumchloride and the like; herpes treatment drugs, such asO-[(2-hydroxyethoxy)methyl]guanine; psoriasis, seborrhea and scabicideagents, such as shale oil and derivatives thereof, elubiol,ketoconazole, coal tar and petroleum distillates, salicylic acid, zincpyrithione, selenium sulfide, hydrocortisone, sulfur, menthol, psoralen,pramoxine hydrochloride anthralin, and methoxsalen; steroids, such as2-(acetyloxy)-9-fluoro-1′,2′,3′,4′-tetrahydro-11-hydroxypregna-1,4-dieno[16,17-b]naphthalene-3,20-dioneand21-chloro-9-fluoro-1′,2′,3′,4′-tetrahydro-11b-hydroxypregna-1,4-dieno[16z,17-b]naphthalene-3,20-dione, and others including those that areantiinflammatories. Other medicinals include those useful in thetreatment of exposure to poison oak, poison ivy, poison sumac, and thelike. These include camphor, menthol, benzocaine, butamben picrate,dibucaine, dibucaine hydrochloride, dimethisoquin hydrochloride,dyclonine hydrochloride, lidocaine, metacresol, lidocaine hydrochloride,pramoxine hydrochloride, tetracaine, tetracaine hydrochloride, benzylalcohol, camphorated metacresol, juniper tar, phenol, phenolate sodium,resorcinol, diphenhydramine hydrochloride, tripelennamine hydrochloride,hydrocortisone, a corticosteroid, and hydrocortisone acetate. Any othermedication capable of topical administration also can be incorporated ina composition of the present invention in an amount sufficient toperform its intended function.

Anticellulite actives include isobutylmethylxanthine, caffeine,theophylline, theobromine, aminophylline, yohimbine, and mixturesthereof.

Examples of actives suitable for treating hair loss include, but are notlimited to potassium channel openers or peripheral vasodilators such asminoxidil, diazoxide, and compounds such asN*-cyano-N-(tert-pentyl)-N′-3-pyridinyl-guanidine (“P-1075”) asdisclosed in U.S. Pat. No. 5,244,664, which is incorporated herein byreference; vitamins, such as vitamin E and vitamin C, and derivativesthereof such as vitamin E acetate and vitamin C palmitate; hormones,such as erythropoietin, prostaglandins, such as prostaglandin EI andprostaglandin F2-alpha; fatty acids, such as oleic acid; diruretics suchas spironolactone; heat shock proteins (“HSP”), such as HSP 27 and HSP72; calcium channel blockers, such as verapamil HCL, nifedipine, anddiltiazemamiloride; immunosuppressant drugs, such as cyclosporin andFk-506; 5 alpha-reductase inhibitors such as finasteride; growth factorssuch as, EGF, IGF and FGF; transforming growth factor beta; tumornecrosis factor; non-steroidal anti-inflammatory agents such asbenoxaprofen; retinoids such as tretinoin; cytokines, such as IL-6, IL-1alpha, and IL-1 beta; cell adhesion molecules such as ICAM;glucorcorticoids such as betametasone; botanical extracts such as aloe,clove, ginseng, rehmannia, swertia, sweet orange, zanthoxylum, Serenoarepens (saw palmetto), Hypoxis rooperi, stinging nettle, pumpkin seeds,and rye pollen; other botanical extracts including sandlewood, red beetroot, chrysanthemum, rosemary, burdock root and other hair growthpromoter activators which are disclosed in DE 4330597 which isincorporated by reference in its entirety herein; homeopathic agentssuch as Kalium Phosphoricum D2, Azadirachta indica D2, and Joborandi DI;genes for cytokines, growth factors, and male-pattered baldness;antifungals such as ketoconazole and elubiol; antibiotics such asstreptomycin; proteins inhibitors such as cycloheximide; acetazolamide;benoxaprofen; cortisone; diltiazem; hexachlorobenzene; hydantoin;nifedipine; penicillamine; phenothaiazines; pinacidil; psoralens,verapamil; zidovudine; alpha-glucosylated rutin having at least one ofthe following rutins: quercetin, isoquercitrin, hespeddin, naringin, andmethylhesperidin, and flavonoids and transglycosidated derivativesthereof which are all disclosed in JP 7002677, which is incorporated byreference in its entirety herein; and mixtures thereof. Preferred hairloss treatment agents include minoxidil,6-(1-piperdinyl)-2,4-pyrimidinediamine-3-oxide,N′-cyano-N-(tert-pentyl)-N′-3-pyridinyl-guanidine, finasteride,retinoids and derivatives thereof, ketoconazole, elubiol or mixturesthereof.

Examples of actives suitable for use in inhibiting hair growth include:serine proteases such as trypsin; vitamins such as alpha-tocophenol(vitamin E) and derivatives thereof such as tocophenol acetate andtocophenol palmitate; antineoplastic agents, such as doxorubicin,cyclophosphamide, chlormethine, methotrexate, fluorouracil, vincristine,daunorubicin, bleomycin and hydroxycarbamide; anticoagulants, such asheparin, heparinoids, coumaerins, detran and indandiones; antithyroiddrugs, such as iodine, thiouracils and carbimazole; lithium and lithiumcarbonate; interferons, such as interferon alpha, interferon alpha-2aand interferon alpha-2b; retinoids, such as retinol (vitamin A),isotretinoin: glucocorticoids such as betamethasone, and dexamethosone;antihyperlipidaemic drugs, such as triparanol and clofibrate; thallium;mercury; albendazole; allopurinol; amiodarone; amphetamines; androgens;bromocriptine; butyrophenones; carbamazepine; cholestyramine;cimetidine; clofibrate; danazol; desipramine; dixyrazine; ethambutol;etionamide; fluoxetine; gentamicin, gold salts; hydantoins; ibuprofen;impramine; immunoglobulins; indandiones; indomethacin; intraconazole;levadopa; maprotiline; methysergide; metoprolol; metyrapone; nadolol;nicotinic acid; potassium thiocyanate; propranolol; pyridostimine;salicylates; sulfasalazine; terfenadine; thiamphenicol; thiouracils;trimethadione; troparanol; valproic acid; and mixtures thereof.Preferred hair growth inhibitory agents include serine proteases,retinol, isotretinoin, betamethoisone, alpha-tocophenol and derivativesthereof, or mixtures thereof.

Examples of hair bleaching agents include perborate or persulfate salts.

Deodorant compounds include astringent salts and bioactive compounds.The astringent salts include organic and inorganic salts of aluminum,zirconium, zinc, and mixtures thereof. The anion of the astringent saltcan be, for example, sulfate, chloride, chlorohydroxide, alum, formate,lactate, benzyl sulfonate or phenyl sulfonate. Exemplary classes ofantiperspirant astringent salts include aluminum halides, aluminumhydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides, andmixtures thereof. Exemplary aluminum salts include aluminum chloride andthe aluminum hydroxyhalides having the general formula Al₂(OH)_(x)Q_(y)XH₂Q, wherein Q is chlorine, bromine or iodine; x is about2 to about 5; x+y is about 6, wherein x and y are not necessarilyintegers; and X is about 1 to about 6. Exemplary zirconium compoundsinclude zirconium oxy salts and zirconium hydroxy salts, also referredto as zirconyl salts and zirconyl hydroxy salts, and represented by thegeneral empirical formula ZrO(OH)₂-nz L_(z), wherein z varies from about0.9 to about 2 and is not necessarily an integer; n is the valence of L;2-nz is greater than or equal to 0; and L is selected from the groupconsisting of halides, nitrate, sulfamate, sulfate, and mixturesthereof.

Exemplary deodorant compounds therefore include, but are not limited to,aluminum bromohydrate, potassium alum, sodium aluminum chlorohydroxylactate, aluminum sulfate, aluminum chlorohydrate, aluminum-zirconiumtetrachlorohydrate, an aluminum-zirconium polychlorohydrate complexedwith glycine, aluminum-zirconium trichlorohydrate, aluminum-zirconiumoctachlorohydrate, aluminum sesquichlorohydrate, aluminumsesquichlorohydrex PG, aluminum chlorohydrex PEG, aluminum zirconiumoctachlorohydrex glycine complex, aluminum zirconium pentachlorohydrexglycine complex, aluminum zirconium tetrachlorohydrex glycine complex,aluminum zirconium trichlorohydrex glycine complex, aluminumchlorohydrex PG, zirconium chlorohydrate, aluminum dichlorohydrate,aluminum dichlorohydrex PEG, aluminum dichlorohydrex PG, aluminumsesquichlorohydrex PG, aluminum chloride, aluminum zirconiumpentachlorohydrate, numerous other useful antiperspirant compoundslisted in the CTFA Handbook at p. 56, incorporated herein by reference,and mixtures thereof.

In addition to the astringent salts, the deodorant compound can be abacteriostatic quaternary ammonium compound, such as, for example, cetyltrimethyl ammonium bromide, cetyl pyridinium chloride, benzethoniumchloride, diisobutylbenzoxyethoxyethyldimethylbenzyl ammonium chloride,sodium N-lauryl sarcosine, sodium N-polymethyl sarcosine, lauroylsarcosine, N-myristolyl glycine, potassium N-lauroyl sarcosine, andstearyl trimethyl ammonium chloride; or a bioactive compound; or acarbonate or bicarbonate salt, such as, for example, the alkali metalcarbonates and bicarbonates, and the ammonium and tetralkylammoniumcarbonates and bicarbonates. Other useful deodorant compounds includechlorophyllin copper complex, aluminum chloride, aluminum chloridehexahydrate, and methylbenzethonium chloride.

Antioxidants are also useful in formulations of the invention. Typicalsuitable antioxidants include propyl, octyl and dodecyl esters of gallicacid, butylated hydroxyanisole (BHA, usually purchased as a mixture ofortho and meta isomers), butylated hydroxytoluene (BHT),nordihydroguaiaretic acid, Vitamin A, ascorbic acid and its salts,ascorbyl esters of fatty acids, ascorbic acid derivatives (e.g.,magnesium ascorbyl phosphate, sodium ascorbyl phosphate, ascorbylsorbate), tocopherol, tocopherol acetate, other esters of tocopherol,tocotrienols and their esters, and6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (commerciallyavailable under the tradename TROLOX). Other suitable antioxidantsinclude uric acid and its salts and alkyl esters, sorbic acid and itssalts, lipoic acid, amines (e.g., N,N-diethylhydroxylamine,amino-guanidine), sulfhydryl compounds (e.g., glutathione, N-acetylcysteine), dihydroxy fumaric acid and its salts, lycine pidolate,arginine pilolate, nordihydroguaiaretic acid, bioflavonoids, curcumin,lysine, methionine, proline, superoxide dismutase, silymarin, teaextracts, grape skin/seed extracts, melanin, and rosemary extracts maybe used.

Preferred antioxidants are photostable antioxidants. An exemplaryphotostable antioxidant is marketed under the tradename EMBLICA by EMDChemicals. See, e.g., U.S. Pat. No. 6,831,191. Antioxidants, preferablyphotostable antioxidants (e.g., EMBLICA), may be included in sunscreenadditives at about 0.05 to about 5%, or about 0.05 to about 2%, or about0.1%, 0.2%, 0.3%, or 0.4%, or in sunscreen/bodywashes at about 0.02 toabout 2%, or about 0.02 to about 1%, or about 0.04%, 0.06%, 0.08%, 0.1%,0.2%, or 0.3%.

Insect repellants include the most widely used active agent for personalcare products, N,N-Diethyl-m-toluamide, frequently called “DEET” andavailable in the form of a concentrate containing at least about 95percent DEET. Other synthetic chemical repellents include dimethylphthalate, ethyl hexanediol, indalone, di-n-propylisocinchoronat-e,bicycloheptene, dicarboximide and tetrahydrofuraldehyde. Certainplant-derived materials also have insect repellent activity, includingcitronella oil and other sources of citronella (including lemon grassoil), limonene, rosemary oil and eucalyptus oil. Choice of an insectrepellent for incorporation into compositions of the invention willfrequently be influenced by the odor of the repellent. The amount ofrepellent agent used will depend upon the choice of agent; DEET isuseful at high concentrations, such as up to about 15 percent or more,while some of the plant-derived substances are typically used in muchlower amounts, such as 0.1 percent or less

The compositions of the present invention may contain a wide range ofadditional active components. The CTFA Cosmetic Ingredient Handbook,Seventh Edition, 1997 and the Eighth Edition, 2000, which areincorporated by reference herein in its entirety, describes a widevariety of active ingredients commonly used in skin care compositions,which are suitable for use in the compositions of the present invention.Other topically-active compounds are listed in Remington'sPharmaceutical Sciences, 20th Ed., Lippincott Williams & Witkins,Baltimore, Md. (2000) (hereinafter Remington's), U.S. Pharmacopeia andNational Formulary, The United States Pharmacopeial Convention, Inc.,Rockville, Md. and Physician's Desk Reference, Medical Economics Co.,Inc., Oradell, N.J. incorporated herein by reference.

The non-sunscreen active may be provided as is or in encapsulated form.Encapsulation is described for sunscreen additives, above. Besides theencapsulated active, in some embodiments an additive or composition fortopical application containing the active further includes a cationicpolymer, as described herein, as well as, optionally, a film former, apreservative, and/or an antioxidant that is stable upon exposure tosunlight. Other components may be as described herein. In someembodiments the additive or composition for topical application maycomprise two, three, four, five, six, seven, eight, nine, ten, or morethan ten actives, each of which may be encapsulated or non-encapsulated,in any combination.

In preferred embodiments, the active is encapsulated sol-gelmicrocapsules, such as silica sol-gel microcapsules. Such microcapsulesare described in U.S. Pat. Nos. 6,238,650; 6,436,375, 6,303,149; and6,468,509. Thus, in some embodiments the invention provides an additivefor addition to a composition for topical application, where theadditive comprises an encapsulated non-sunscreen active, and optionallyfurther comprises a cationic polymer. In other embodiments the inventionprovides a composition for topical application that contains anadditive, where the additive comprises an encapsulated non-sunscreenactive, and optionally further comprises a cationic polymer. Furtheringredients include film formers, antioxidants, preservatives, and otheringredients as listed herein. The composition for topical applicationmay be, e.g., a bodywash.

In some embodiments the invention provides microcapsules, e.g., sol-gelmicrocapsules (e.g., as described in U.S. Pat. Nos. 6,238,650;6,436,375, 6,303,149; and 6,468,509) that act as a protective barrier onthe skin when used either alone, or as an additive in a bodywash. Inthese embodiments, the sol-gel microcapsules may be used without anyadditional active ingredients (i.e., empty), providing a physicalbarrier, or they may be used with additional encapsulated activeingredients that enhance their barrier function. For example, themicrocapsules may contain substances that act to screen toxic agents(e.g., biological or chemical warfare agents) or radiation (e.g., alpha,beta, or gamma radiation) partially or completely from penetrating theuser's skin. In some embodiments, the microcapsules may contain one ormore agents that absorb radiation, such as graphite, lead, tungsten, andothers known in the art, or agents that reflect radiation such asceramic beads. As the microcapsules may be designed so as to experienceminimal or no breakage when applied to the skin, as well as toexperience minimal penetration of the skin, it is possible to use eventoxic substances (e.g., lead) that provide a screening effect, sincethese substances will not be released or will be released in onlyminimal amounts. The microcapsules are eventually removed from the skinthrough repeated washing and/or normal sloughing of the external skincell layers. Especially for agents used for one-time or very fewexposures, such as can occur for personnel engaged in combating orcontaining terrorist attacks or in warfare, the invention provides ameans to deliver a last line of defense on the skin of personnel wherethe active used in the microcapsules may be one that is not appropriatefor long-term use, but that is appropriate for a limited number ofapplications in order to protect the wearer from a greater risk (e.g.,microcapsules encapsulating lead to protect against a radiation attack).

The microcapsules, e.g., sol-gel microcapsules, can be prepared so as toexperience no or minimal breakage when applied to the skin, either as isor in the form of a bodywash. Alternatively, the microcapsules, e.g.,sol-gel microcapsules, can be prepared so as to experience variousdegrees of breakage, on average, when applied as is or in a bodywash.Thus, the microcapsules, e.g., sol-gel microcapsules, may be prepared soas to experience about 0% breakage, or breakage in a range from about0.1, 0.5, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90% to about 0.5,1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90%, after application (orapplication and rinsing in the case of a bodywash containing themicrocapsules). Furthermore, the microcapsules may be formulated so asto break open in response to conditions that occur on the skin, so thatafter application the microcapsules act to release their contents in atime-release or controlled manner. Non-limiting exemplary skin or hairconditions that can vary with the user's environment, the variation ofwhich can trigger breakage of microcapsules, include pH, temperature,friction, exposure to light or air, pressure, and the like.

C. Cationic Component

In some embodiments the additives, e.g., sunscreen additives andsunscreen/bodywashes of the invention further include a cationiccomponent. Without being bound by theory, it is thought that thiscomponent serves as a protein binder, to provide a positive charge topromote attachment of the composition to proteins of the skin and hair,thus increasing retention of the components, e.g., sunscreen, afterrinse and during normal activities. This positive charge creates astrong affinity for the protein in the hair or skin. Any means ofimparting a positive charge may be used.

Preferred means are by including one or more cationic polymers in thecomposition. Various cationic polymers may be used. Examples of cationicpolymers are described in U.S. Pat. Nos. 6,224,852; 3,816,616;4,272,515; 4,298,494; 4,080,310; 4,048,301; 4,009,256; and 3,186,911.Cationic polymers are available commercially, e.g., from Union CarbideCorp. under the trademark POLYMER JR., from Celanese-Stein Hall underthe trademark JAGUAR, from GAF Corporation under the tradename Gafquatmand from Merck & Co., Inc under the trademark MERQUAT by. Representativeone are Merquat 100, a highly charged cationic dimethyldiallylammoniumchloride homopolymer, and Merquat™ 550, a highly charged cationiccopolymer prepared with dimethyldiallylammonium chloride and acrylamide.These materials are designated in the CTFA dictionary as Quaternium40and Quaternium-41, respectively.

Especially preferred are polyquaterniums. Quaternized material in powderform, not limited to the polyquaterniums, may also be used. Exemplarypolyquaterniums of use in the invention include polyquaternium-4, -7,-11, -22, -37, -44, -51, and -64. Polyquaternium compounds are availablecommercially, e.g., CELQUAT L-200 for polyquaternium-4. Without beinglimited by theory, it is thought that with the trapping of theencapsulate (e.g., sunscreen active inside the capsule) by this cationiccomponent. rinse off is difficult and renders the active substantive tothe protein in the skin and hair.

Useful in some embodiments of the invention is a dry cationic component,such as sold under the tradename CAE (Anjinomoto Co., Inc.), containingDL-pyrrolidone Carboxylic acid salt of L-Cocoyl Arginine Ethyl Ester,which is a cationic agent useful for binding to proteins and providingan antimicrobial effect.

In some embodiments of additives, e.g., sunscreen additives, thecationic component (e.g., cationic polymer) comprises about 0.1 to about20%, or about 0.1 to about 10%, or about 0.5 to about 10%, or about 1 toabout 10%, or about 0.5 to about 5%, or about 0.5 to about 3% or about 1to about 5%, or about 1 to about 3%, or about 1% of the totalcomposition. In some embodiments, the cationic component ispolyquaternium-4; in some embodiments the polyquaternium-4 is present atabout 1%.

In some embodiments of active/bodywashes, e.g., sunscreen/bodywashes,the cationic component (e.g., cationic polymer) comprises about 0.03 toabout 7%, or about 0.03 to about 4%, or about 0.2 to about 4%, or about0.3 to about 4%, or about 0.2 to about 2%, or about 0.3 to about 4%, orabout 0.3 to about 1%, or about 0.3 or 0.4% of the total composition. Insome embodiments, the cationic component is polyquaternium-4; in someembodiments the polyquaternium-4 is present at about 0.33%.

D. Film Formers

In some embodiments, compositions of the invention further include acomponent that provide a film barrier system, typically a hydrophobiclayer that serves to maintain the residual sunscreen after rinse. Filmbarrier systems are well-known in the art and include, withoutlimitation, petrolatum, silicon derivatives, and combinations thereof.Also useful are polymers with carboxylic ends which render themselvesinsoluble until neutralized. After being neutralized they can act asfilm formers. Film formers also include emollient esters, lanolinderivatives (e.g., acetylated lanolins), and superfatted oils. Filmformers are available commercially, e.g., a preferred film former isMOISTUREGUARD™, which contains petrolatum, dimethicone, stearamidopropyldimethylamine stearate, and tocopheryl acetate, available fromEngelhard.

It may also be desirable to add acrylic co-polymers to the formulationsof the invention as film formers. An exemplary liquid acrylic copolymerformulation is DERMACRYL, marketed by National Starch and Chemical.Acrylic co-polymers may be included in sunscreen additives at about 0.1to about 5%, or about 0.2 to about 3%, or about 0.2%, 0.3%, 0.4%, or0.5%, or in sunscreen/bodywashes at about 0.05 to about 2%, or about 0.1to about 1%, or about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%.

A secondary film former may also be used, e.g., keratin or other proteinderivative in an amino acid complex such as cysteine.

The film former may be present in the sunscreen additive in the range ofabout 0.1 to about 25%, or about 1 to about 10%; or about 2 to about 6%;or about 3, 4, or 5%. In some embodiments, the film former MoistureGuardis used at a concentration of about 4.2%. Equivalent film formers, atequivalent concentrations, may also be used.

As noted, some preparations may perform more than one function, forexample, inorganic blockers such as Tioveil and Spectraveil (both of theTioxide Group), in certain variations, may be film-formers and may haveadvantageous uses here.

In addition, many emollients may also perform a film former function inthat they provide a barrier on the skin. Thus, compositions of theinvention may include water-insoluble emollients that include fattyacids such as oleic and stearic; fatty alcohols such as cetyl, andhexadecyl (ENJAY); esters such as diisopropyl adipate, benzoic acidesters of C₉–C₁₅ alcohols, and isononyl iso-nonanoate; alkanes such asmineral oil; silicones; such as dimethyl polysiloxane and ethers such aspolyoxypropylene butyl ethers and polyoxypropylene cetyl ethers. If awater-insoluble emollient is used it may be in an amount from about 2%to about 15% by weight, and most preferably from about 4% to about 10%.

Other useful film formers include polythylenes, such as those availablefrom New Phase Technologies as PERFORMALENE 400, a polyethylene having amolecular weight of 400. Another suitable water-proofing agent ispolyethylene 2000 (molecular weight of 2000), which is available fromNew Phase Technologies as PERFORMALENE 2000.

Yet another suitable film former/waterproofing agent is synthetic wax,also available from New Phase Technologies as PERFORMA V-825. Still yetanother suitable film former/waterproofing agent is octadecene/MAcopolymer

Additional film formers which also may be used within the framework ofthe invention include any film former chemistry known in the art. Thus,suitable additional film formers include acacia gum, cellulosederivatives, guar derivatives and all those set forth on pages 68–69 ofthe C.T.F.A. Cosmetic Ingredient Handbook, First Edition, 1988, which ishereby incorporated by reference. Such film formers include acrylamidescopolymer, acrylamide/sodium acrylate copolymer, acrylate/acrylamidecopolymer, acrylate/ammonium methacrylate copolymer, acrylatescopolymer, acrylates/diacetoneacrylamide copolymer, acrylic/acrylatecopolymer, adipic acid/dimethylaminohydroxypropyl diethlenetnaminecopolymer, adipic acid/epoxypropyl/diethlenetriamine copolymer, albumen,allyl stearate/VA copolymer, aminoethylacrylate phosphate/acrylatecopolymer, ammonium acrylates copolymer, ammonium alginate, ammoniumvinyl acetate/acrylates copolymer, AMP acrylates/diacetoneacrylamidecopolymer, balsam canada, balsam oregon, balsam peru, balsam tolu,benzoi acid/phthalic anhydride/pentaerythritol/neopentyl glycol/palmiticacid copolymer, benzoin extract, butadiene/acrylonitrile copolymer,butylated urea-formaldehyde resin, butyl benzoic acid/phthalic anhydridetrimethylolethane copolymer, butyl ester of ethylene maleic anhydridecopolymer, butyl ester of PVM/MA copolymer, calcium carrageenean,calcium/sodium PVM/MA copolymer, carboxymethyl hydroxyethyl cellulose,cellulose gum, collodion, copal, corn starch/aciylainide/sodium acrylatecopolymer, damar, diethylene glycolamine/epichlorohydrin/piperazinecopolymer, DMJ-IF, dodecanedoic acid/cetearyl alcoholglycol copolymer,ethylcellulose, ethylene/acrylate copolymer, ethylene/maleic anhydridecopolymer, ethylene/vinyl acetate copolymer, ethyl ester of PVM/fvIAcopolymer, flexible collodian, gum benzoin, gutta percha, hydroxybutylmethylceflulose, hydroxyethylcellulose, hydroxyethyl ethyl cellulose,hydroxypropylcellulose, hydroxypropyl guar, hydroxypropylmethylcellulose, isopropyl ester of PVM/MA copolymer, maltodextrin,melamine/formaldehyde resin, methacryloyl ethyl betainelmethacrylatescopolymer, nitrocellulose,octylacrylamide/acrylates/butylaminoethylmethaciylate copolymer,octylacrylamide/acrylates copolymer, phthalic anhydride/glycerin/gycidyldecanoate copolymer, phthalic/trimellitic/glycols copolymer,polyacrylamide, polyaciylamidomethylpropane sulfone acid, polyacrylicacid, polybutylene terephthalate, polychlorotrifluoroethylene,polyethylacrylate, polyethylene, polyethylene terephthalate,polyisobutene, Polyquaternium-1, Polyquaternium-2, Polyquaternium-4,Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8,Polyquaternium-9, Polyquaternium-10, Polyquaternium-11,Polyquaternium-12, Polyquaternium-13, Polyquaternium-14,Polyquaternium-15, polystyrene, polyvinyl acetate, polyvinyl alcohol,polyvinyl butyral, polyvinyl imidazolinium acetate, polyvinyl laurate,polyvinyl methyl ether, potassium carrageenan, PVM/MA copolymer, PVP,PVP/dimethylaminoethymethacrylate copolymer, PVP/eicosene copolymer,PVP/ethyl methacrylate/methacrylic acid copolyerm, PVP/hexadecenecopolymer, PVP/VA copolymer, PVP/vinyl acetate/itaconic acid copolymer,rosin, serum albumin, shellac, sodium acrylate/vinyl alcohol, copolymer,sodium carrageen, sodium polymethacrylate, sodium polystyrene sulfonate,starch/acrylates/acrylamide copolymer, starch diethylaminoethyl ether,steaxyvinyl ether/maleic anhydride copolymer,styrene/acrylate/acrylonitrile copolymer, styrene/acrylate/ammoniummethacrylate copolymer, styrene/maleic anhydride copolymer, styrene/PVPcopolymer, sucrose benzoate/sucrose acetate isobutyrate/butyl benzylphthalate copolymer, sucrose benzoate/sucrose acetate isobutyrate/butylbenzyl phthalate/methyl methaciylate copolymer, sucrose benzoate/sucroseacetate isobutyrate copolymer, toluenesulfonamide/formaldehyde resin,tragacath gum, vinyl acetate/crotonates copolymer, vinylacetate/crotonic acid copolymer, vinyl acetate/crotonicacid/methacryloxybenzophenon-1 copolymer, vinyl acetate/crotonicaid/vinyl neodecanoate copolymer, and zein

Additional film formers include those set forth in U.S. Pat. Nos.6,838,419; 6,838,088; 6,780,422; 6,531,118; and 5,916,541, all of whichare incorporated herein by reference

E. Other Components

A wide variety of additional components may be added to the compositionsof the present invention, as long as the components are selected so asto avoid any undesirable reaction with the primary components (e.g., oneor more of the sunscreen agents) of the composition. The CTFA CosmeticIngredient Handbook, Seventh Edition, 1997 and the Eighth Edition, 2000(incorporated by reference herein), provide a broad source of possiblecosmetic and pharmaceutical ingredients typically used in skin carecompositions. Examples of such additional components include one or moreof the following: Absorbents, abrasives, anticaking agents, antifoamingagents, binders, biological additives, buffering agents, bulking agents,chelating agents/sequestrants (e.g., disodium EDTA), chemical additives,colorants, cosmetic astringents, cosmetic biocides, denaturants, drugastringents, emollients (including glycerin alovera, and Vitamins A, C,and D [hydrating agents and skin protectants]), foam boosters, fragrancecomponents, gums, humectants/moisturizers (including urea, guanidine,glycolic acid, polyhydroxy alcohols such as sorbitol, glycerin,hexanetriol, propylene glycol, hexylene glycol and the like,polyethylene glycol, sugars and starches, sugar and starch derivatives,D-panthenol, hyaluronic acid, lactamide monoethanolamine, acetamidemonoethanolamine, and mixtures thereof), hydrotropes, neutralizingagents, opacifying agents and pigments, pH adjusters, plasticizers,preservatives, propellants, reducing agents, skin bleaching agents, skinprotectants, solubilizing agents, and suspending agents (e.g., Carbomer1382).

In some embodiments, the additives and bodywashes of the invention,e.g., sunscreen additives or sunscreen/bodywashes include apreservative. Exemplary preservatives useful in the invention includecitric acid, tartaric acid, phosphoric acid, iminodiacetic acid,nitrilotriacetic acid, hydroxyethyleneaminodiacetic acid andethylenediaminetetraacetic acid and salts thereof; para-hydroxybenzoatessuch as butyl paraben, methyl paraben and propyl paraben; imidazolines(e.g., imidiazolinylurea), triclosan, hydantoins (e.g.,dimethyloldimethylhydantoin), isothiazolidinone compounds and mixturesthereof. Commercially available preservatives include KATHON CG andKATHON CGII, which contain methylchloroisothiazolinone andmethylisothiazolinone (Rohm and Haas). When present, the quantity ofpreservative is in the range from 0.001 to 2%, preferably from 0.01 to0.2%.

In certain embodiments the compositions of the invention include achelating agent. Chelating agents are substances used to chelate or bindmetallic ions, such as with a heterocyclic ring structure so that theion is held by chemical bonds from each of the participating rings.Suitable chelating agents include ethylene diaminetetraacetic acid(EDTA), EDTA disodium, calcium disodium edetate, EDTA trisodium, EDTAtetrasodium and EDTA dipotassium. One or more chelating agents canoptionally be included in the additives or additive/bodywashes inamounts ranging from about 0.001 to about 0.2 weight percent, or about0.01% weight percent.

Thickening agents or gellants may be added as desired to adjust thetexture and viscosity of the composition. Exemplary agents or gellantsmay be selected from Carbopol™ resins [e.g., 934, 971, 974, 980, 981]and Pemulen™ [TR-1 and TR-2][both Carbopol™ and Pemulen™ are registeredtrademarks of BF Goodrich], Noveon AA-1, ETD resins, and Ultrez™ resins[registered trademark, BF Goodrich]. In addition, carbomers might beuseful for this purpose.

It may be desired to include a non-polar wax. Examples of such usefulwaxes include ester waxes, diester waxes, hydrocarbon waxes, siliconewaxes and triglyceride waxes and mixtures thereof.

Other components may include a liquid hydrocarbon (similar to pentane),and/or a cationic foaming agent derived from arginine and or cysteine.

Further optional ingredients which can be present in the compositioninclude fragrance, dyes, antimicrobial materials such as triclocarban,triclosan, iodophors, iodine formulations, phenolic compounds, e.g.hexachlorophene, and bisbiguanides, e.g. chlorhexidene gluconate, andthe like. See, e.g., U.S. Pat. Nos. 6,827,795; 6,517,854; 6,010,817;5,173,216; 5,719,113; 5,259,984; 5,562,912; 5,629,006; 5,728,662;5,767,163; 5,750,579; 5,591,442; 5,650,143; 5,772,640; and 4,478,821.

The components of the composition are generally mixed in water.

F. Surfactants and Bodywashes

Compositions of the invention may be formulated as products for washingthe skin, for example, bath or shower gels, hand washing compositions orfacial washing liquids; pre- and post-shaving products; rinse-off,wipe-off and leave-on skin care products; products for washing the hairand for dental use. Shower gels are particularly preferred productforms.

If it is desired to prepare a sunscreen/bodywash composition, thesunscreen additives of the invention may be combined with otheringredients to produce a bodywash (e.g., a liquid or solid formulation).The sunscreen/bodywash may include one or more surfactants. The use ofsurfactants in bodywashes is well-known in the art. Any surfactant knownin the art and appropriate for a bodywash composition may be used. See,McCutcheon's Detergents & Emulsifiers, M.C. Publishing Co. (NorthAmerican edition 1989); Schwartz, et al., Surface Active Agents, TheirChemistry and Technology, New York, Interscience Publishers, 1949, andU.S. Pat. Nos. 6,096,697; 4,741,855; 4,788,066; 5,104,646; 5,106,609;2,658,072; 2,438,091; 2,528,378; 2,486,921; 2,486,922; 2,396,278;2,979,465; 3,179,599; 5,322,643; 5,084,212; 3,332,880; 4,122,029;4,265,878; 4,421,769; 3,929,678; 3,959,461; 4,387,090; 4,303,543; and6,224,852; and in British Patent Nos. 848,224 and 791,415. Also see CTFACosmetic Ingredient Dictionary, 4^(th) Edition 1991, pages 509–514 forvarious long chain alkyl cationic surfactants; and Richmond, James M.,Cationic Surfactants, Marcel Dekker, Inc., New York and Basel, 1990.

The surfactant(s) may be cationic, anionic, nonionic, zwitterionic,amphoteric, or any combination thereof.

Specific examples of anionic surfactants include those selected from thegroup consisting of alkyl and alkyl ether sulfates, sulfatedmonoglycerides, sulfonated olefins, alkyl aryl sulfonates, primary orsecondary alkane sulfonates, alkyl sulfosuccinates, acyl taurates, acylisethionates, alkyl glycerylether sulfonate, sulfonated methyl esters,sulfonated fatty acids, alkyl phosphates, ethoxylated alkyl phosphates,acyl glutamates, acyl sarcosinates, alkyl sulfoacetates, acylatedpeptides, alkyl ether carboxylates, acyl lactylates, anionicfluorosurfactants, and combinations thereof. Combinations of anionicsurfactants can be used effectively in the present invention. Specificexamples of alkyl sulfates that may be used are sodium, ammonium,potassium, magnesium, or TEA salts of lauryl or myristyl sulfate.Examples of alkyl ether sulfates that may be used include ammonium,sodium, magnesium, or TEA laureth-3 sulfate.

Another suitable class of anionic surfactants are the sulfatedmonoglycerides of the form R1CO—O—CH₂—C(OH)H—CH₂—O—SO₃M, wherein R1 is asaturated or unsaturated, branched or unbranched alkyl group from about8 to about 24 carbon atoms, and M is a water-soluble cation such asammonium, sodium, potassium, magnesium, triethanolamine, diethanolamineand monoethanolamine. An example of a sulfated monoglyceride is sodiumcocomonoglyceride sulfate.

Other suitable anionic surfactants include olefin sulfonates of the formR1 SO₃M, wherein R1 is a mono-olefin having from about 12 to about 24carbon atoms, and M is a water-soluble cation such as ammonium, sodium,potassium, magnesium, triethanolamine, diethanolamine andmonoethanolamine. An example of a sulfonated olefin is sodium C14/C16alpha olefin sulfonate.

Other suitable anionic surfactants are the linear alkylbenzenesulfonates of the form R1—C₆H₄—SO₃M, wherein R1 is a saturated orunsaturated, branched or unbranched alkyl group from about 8 to about 24carbon atoms, and M is a water-soluble cation such as ammonium, sodium,potassium, magnesium, triethanolamine, diethanolamine andmonoethanolamine. An example of this anionic surfactant is sodiumdodecylbenzene sulfonate.

Still other anionic surfactants suitable for the compositions of thepresent invention include the primary or secondary alkane sulfonates ofthe form R1SO₃M, wherein R1 is a saturated or unsaturated, branched orunbranched alkyl chain from about 8 to about 24 carbon atoms, and M is awater-soluble cation such as ammonium, sodium, potassium, magnesium,triethanolamine, diethanolamine and monoethanolamine. An example of analkane sulfonate useful herein is alkali metal or ammonium C13–C17paraffin sulfonates.

Still other suitable anionic surfactants are the alkyl sulfosuccinates,which include disodium N-octadecylsulfosuccinamate; diammonium laurylsulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinate; diamyl ester of sodiumsulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; anddioctyl esters of sodium sulfosuccinic acid.

Also useful are taurates that are based on taurine. Examples of tauratesinclude N-alkyltaurines such as the one prepared by reactingdodecylamine with sodium isethionate as detailed in U.S. Pat. No.2,658,072.

Another class of suitable anionic surfactants is the acyl isethionates.Nonlimiting examples of these acyl isethionates include ammonium cocoylisethionate, sodium cocoyl isethionate, sodium lauroyl isethionate, andmixtures thereof.

Still other suitable anionic surfactants are the alkylglyceryl ethersulfonates of the form R1-OCH₂—C(OH)H—CH₂—SO₃M, wherein R1 is asaturated or unsaturated, branched or unbranched alkyl group from about8 to about 24 carbon atoms, and M is a water-soluble cation such asammonium, sodium, potassium, magnesium, triethanolamine, diethanolamineand monoethanolamine. One example is sodium cocoglyceryl ethersulfonate.

Other suitable anionic surfactants include: Sulfonated fatty acids ofthe form R1-CH(SO₄)—COOH and sulfonated methyl esters of the fromR1-CH(SO₄)—CO—O—CH₃, where R1 is a saturated or unsaturated, branched orunbranched alkyl group from about 8 to about 24 carbon atoms (e.g.,alpha sulphonated coconut fatty acid and lauryl methyl ester);phosphates such as monoalkyl, dialkyl, and trialkylphosphate saltsformed by the reaction of phosphorous pentoxide with monohydric branchedor unbranched alcohols having from about 8 to about 24 carbon atoms(e.g., sodium mono or dilaurylphosphate, ethoxylated monoalkylphosphates, etc.); acyl glutamates corresponding to the formulaR1CO—N(COOH)—CH₂CH₂—CO₂M wherein R1 is a saturated or unsaturated,branched or unbranched alkyl or alkenyl group of about 8 to about 24carbon atoms, and M is a water-soluble cation (e.g., sodium lauroylglutamate and sodium cocoyl glutamate); alkanoyl sarcosinatescorresponding to the formula R1CON(CH₃)—CH₂CH₂—CO₂M wherein R1 is asaturated or unsaturated, branched or unbranched alkyl or alkenyl groupof about 10 to about 20 carbon atoms, and M is a water-soluble cation(e.g., sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, andammonium lauroyl sarcosinate); alkyl ether carboxylates corresponding tothe formula R1-(OCH₂CH₂)x—OCH₂—CO₂M wherein R1 is a saturated orunsaturated, branched or unbranched alkyl or alkenyl group of about 8 toabout 24 carbon atoms, x is 1 to 10, and M is a water-soluble cation(e.g., sodium laureth carboxylate); acyl lactylates corresponding to theformula R1CO—[O—CH(CH₃)—CO]x—CO₂M wherein R1 is a saturated orunsaturated, branched or unbranched alkyl or alkenyl group of about 8 toabout 24 carbon atoms, x is 3, and M is a water-soluble cation (e.g.,sodium cocoyl lactylate); carboxylates, nonlimiting examples of whichinclude sodium lauroyl carboxylate, sodium cocoyl carboxylate, andammonium lauroyl carboxylate; anionic flourosurfactants; and naturalsoaps derived from the saponification of vegetable and/or animal fats &oils examples of which include sodium laurate, sodium myristate,palmitate, stearate, tallowate, cocoate.

Any counter cation, M, can be used on the anionic surfactant.Preferably, the counter cation is selected from the group consisting ofsodium, potassium, ammonium, monoethanolamine, diethanolamine, andtriethanolamine.

Nonlimiting examples of nonionic surfactants that may be included in thecompositions of the present invention include those selected from thegroup consisting of alkyl glucosides, alkyl polyglucosides, polyhydroxyfatty acid amides, alkoxylated fatty acid esters, sucrose esters, amineoxides, and mixtures thereof.

Alkyl glucosides and alkyl polyglucosides are useful herein, and can bebroadly defined as condensation products of long chain alcohols, e.g.,C8–30 alcohols, with sugars or starches or sugar or starch polymers,i.e., glycosides or polyglycosides. These compounds can be representedby the formula (S)_(n)—O—R wherein S is a sugar moiety such as glucose,fructose, mannose, and galactose; n is an integer of from about 1 toabout 1000, and R is a C8–30 alkyl group. Examples of long chainalcohols from which the alkyl group can be derived include decylalcohol, cetyl alcohol, stearyl alcohol, lauryl alcohol, myristylalcohol, oleyl alcohol, and the like. Preferred examples of thesesurfactants include those wherein S is a glucose moiety, R is a C8–20alkyl group, and n is an integer of from about 1 to about 9.Commercially available examples of these surfactants include decylpolyglucoside (available as APG 325 CS from Henkel) and laurylpolyglucoside (available as APG 600CS and 625 CS from Henkel). Alsouseful are sucrose ester surfactants such as sucrose cocoate and sucroselaurate.

Other useful nonionic surfactants include polyhydroxy fatty acid amidesurfactants, more specific examples of which include glucosamidesProcesses for making compositions containing polyhydroxy fatty acidamides are disclosed, for example, in G.B. Pat. Specification 809,060,published Feb. 18, 1959, by Thomas Hedley & Co., Ltd.; U.S. Pat. No.2,965,576, to E. R. Wilson, issued Dec. 20, 1960; U.S. Pat. No.2,703,798, to A. M. Schwartz, issued Mar. 8, 1955; and U.S. Pat. No.1,985,424, to Piggott, issued Dec. 25, 1934.

Other examples of nonionic surfactants include amine oxides. Amineoxides correspond to the general formula R₁, R₂, R₃N→O, wherein R₁contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties,and from 0 to about 1 glyceryl moiety, and R₂ and R₃ contain from about1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g.,methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals. Thearrow in the formula is a conventional representation of a semipolarbond. Examples of amine oxides suitable for use in this inventioninclude dimethyl-dodecylamine oxide, oleyldi(2-hydroxyethyl) amineoxide, dimethyloctylamine oxide, dimethyl-decylamine oxide,dimethyl-tetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamineoxide, di(2-hydroxyethyl)-tetradecylamine oxide,2-dodecoxyethyldimethylamine oxide,3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl)amine oxide,dimethylhexadecylamine oxide.

The term “amphoteric surfactant,” as used herein, is also intended toencompass zwitterionic surfactants, which are well known to formulatorsskilled in the art as a subset of amphoteric surfactants.

A wide variety of amphoteric lathering surfactants can be used in thecompositions of the present invention. Particularly useful are thosewhich are broadly described as derivatives of aliphatic secondary andtertiary amines, preferably wherein the nitrogen is in a cationic state,in which the aliphatic radicals can be straight or branched chain andwherein one of the radicals contains an ionizable water solubilizinggroup, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Nonlimiting examples of amphoteric or zwitterionic surfactants are thoseselected from the group consisting of betaines, sultaines,hydroxysultaines, alkyliminoacetates, iminodialkanoates,aminoalkanoates, and mixtures thereof.

Examples of betaines include the higher alkyl betaines, such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine,lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethylbetaine, cetyl dimethyl betaine (available as Lonzaine 16SP from LonzaCorp.), lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, oleyldimethyl gamma-carboxypropyl betaine, laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethylsulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, laurylbis-(2-hydroxyethyl) sulfopropyl betaine, amidobetaines andamidosulfobetaines (wherein the RCONH(CH.sub.2).sub.3 radical isattached to the nitrogen atom of the betaine), oleyl betaine (availableas amphoteric Velvetex OLB-50 from Henkel), and cocamidopropyl betaine(available as Velvetex BK-35 and BA-35 from Henkel).

Examples of sultaines and hydroxysultaines include materials such ascocamidopropyl hydroxysultaine (available as Mirataine CBS fromRhone-Poulenc).

Examples of amphoteric surfactants of the present invention include thefollowing compounds: Cetyl dimethyl betaine (this material also has theCTFA designation cetyl betaine); Cocamidopropylbetaine; Cocamidopropylhydroxy sultaine. Examples of other useful amphoteric surfactants arealkyliminoacetates, and iminodialkanoates and aminoalkanoates of theformulas RN[(CH₂)CO₂M]₂ and RNH(CH₂)._(m)CO₂M wherein m is from 1 to 4,R is a C₈–C₂₂ alkyl or alkenyl, and M is H, alkali metal, alkaline earthmetal ammonium, or alkanolammonium. Also included are imidazolinium andammonium derivatives. Specific examples of suitable amphotericsurfactants include sodium 3-dodecyl-aminopropionate, sodium3-dodecylaminopropane sulfonate, N-higher alkyl aspartic acids such asthose produced according to the teaching of U.S. Pat. No. 2,438,091; andthe products sold under the trade name “Miranol” and described in U.S.Pat. No. 2,528,378. Other examples of useful amphoterics includeamphoteric phosphates, such as coamidopropyl PG-dimonium chloridephosphate (commercially available as Monaquat PTC, from Mona Corp.).Also useful are amphoacetates such as disodium lauroamphodiacetate,sodium lauroamphoacetate, and mixtures thereof.

In preferred embodiments, the sunscreen/bodywashes of the inventioninclude at least one cationic surfactant. Many cationic surfactants areknown to the art. Suitable cationic surfactants include, but are notlimited to, fatty amines, di-fatty quaternary amines, tri-fattyquaternary amines, imidazolinium quaternary amines, and combinationsthereof. Suitable fatty amines include monalkyl quaternary amines suchas cetyltrimethylammonium bromide. A suitable quaternary amine isdialklamidoethyl hydroxyethylmonium methosulfate. By way of example, thefollowing may be mentioned: stearyldimenthylbenzyl ammonium chloride;dodecyltrimethylammonium chloride; nonylbenzylethyldimethyl ammoniumnitrate; tetradecylpyridinium bromide; laurylpyridinium chloride;cetylpyridinium chloride; laurylpyridinium chloride; laurylisoquinoliumbromide; ditallow(Hydrogenated)dimethyl ammonium chloride;dilauryldimethyl ammonium chloride; and stearalkonium chloride.Additional cationic surfactants are disclosed in U.S. Pat. No. 4,303,543see column 4, lines 58 and column 5, lines 1–42, incorporated herein byreferences. Also see CTFA Cosmetic Ingredient Dictionary, 4th Edition1991, pages 509–514 for various long chain alkyl cationic surfactants;incorporated herein by reference.

The total surfactants, e.g., cationic surfactant, may be present in thesunscreen/bodywash at about 0.1 to about 20%, or about 0.1 to about 10%,or about 0.1 to about 5%, or about 0.5 to about 5%, or about 1 to about10%, or about 1 to about 5%, or about 0.1 to about 2%, or about 1 toabout 2%. In some embodiments, a sunscreen/bodywash composition of theinvention contains a surfactant, e.g., a cationic surfactant, at about1%.

In addition to surfactants, other ingredients, as described above foradditives, may be included in the additive/bodywash. Any component knownin the art or useful in bodywashes may be used.

In some embodiments, soapless cleansers may be used in addition to, orinstead of, soaps/surfactants. For example, Oilatum™ AD (registeredtrademark, Stiefel Laboratories), Aquanil™ (registered trademark, Person& Covey, Inc.), Cetaphil™ (trademark, Galderma Laboratories, Inc.) orSpectroDerm™ (registered trademark, Draxis Pharmaceutical Inc.), ortheir equivalents, may be utilized as a soapless component in thepresent invention.

As noted above, the sunscreen additives of the invention may also becombined with conventional bodywash compositions, as well as withshampoos for hair, and post-wash skincare compositions. Proportions foraddition and mixing are given above as well as in more detail hereafter.An exemplary bodywash that may be used with additives of the inventionis exemplified by SUAVE Body Wash. Ingredients of a typical SUAVEbodywash include: Water, Ammonium Lauryl Sulfate, Ammonium LaurethSulfate, Cocamidopropyl Betaine, Fragrance, Glycerin, Hydrolyzed MilkProtein & Honey Extract, PEG-10 Sunflower Glycerides, Cocamide MEA, GuarHydroxypropylrimonium Chloride, Acrylates Copolymer, PEG-5 Cocamide,Helianthus Annuus (Sunflower) Seed Oil or Glycine Soja (Soybean) Oil,Tetrasoidum EDTA, Propylene Glycol, Ammonium Chloride, Sodium Hydroxide,Methylchloroisothiazolinone, Methylisothiazolinone, Titanium Dioxide (CI77891)

II. Methods

A. Preparation

The compositions of the invention may be prepared by any suitablemethod. In one preferred method, a “Phase I,” which is a “water phase,”is prepared by mixing the more water-soluble components of thecomposition. For example, Polyquaternium-4, a film former (e.g., inMOISTUREGUARD), and encapsulated sunscreen (e.g., in UV PEARLS), may bemixed until uniform. A “Phase II,” which is an “oil phase,” is preparedby mixing the more hydrophobic components of the composition. Forexample, Avobenzone (e.g., PARSOL 1789) may be mixed with Octocrylene,with heating, until dissolved. Then Phase I and Phase II are combinedwith gentle agitation, until a uniform composition is obtained (PhaseIII). Phase III may be further combined with a bodywash composition(e.g., SUAVE bodywash) and mixed until uniform. A further sunscreen,such as titanium dioxide, may be added to the Phase III/bodywashcomposition and mixed until uniform. Alternatively, the sunscreen may beadded before addition to the bodywash or soap to provide an additiveready for formulation with a bodywash or soap.

B. Use

Additives, e.g., sunscreen additives of the invention are generallydesigned to be used in combination with a bodywash. Thus, thecompositions of the invention are typically designed to be applied whilewashing. This characteristic facilitates ease of use and may have theadded benefit of being cumulative. Compositions of the present inventionare readily applied during washing in a suitable or effective amount andmay be generally applied all over the body. Shampoos may be appliedspecifically to the hair. A selected amount of a composition may beapplied directly to the skin or may be used through intermediateapplication to a washcloth, pad, sponge, or other applicator. Afterlathering, dirt and sloughed-off skin may be washed away by rinsing withwater leaving behind one or more of the additives, e.g., sunscreencomponents. Additives of the invention, e.g., sunscreen additives of theinvention are also useful in hair shampoos and conditioners, and inafter-wash lotions.

Thus, methods of the invention include methods for protection of skinfrom sunlight, comprising applying a bodywash comprising a sunscreen tothe skin, wherein after application of the bodywash to skin and rinsing,the skin is protected from sunlight with an average SPF of at leastabout 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20, or more than 20. In some preferred embodiments, the skin isprotected from sunlight with an average SPF of at least about 2. In somepreferred embodiments, the skin is protected from sunlight with anaverage SPF of at least about 5. In some preferred embodiments, the skinis protected from sunlight with an average SPF of at least about 10. Insome preferred embodiments, the skin is protected from sunlight with anaverage SPF of at least about 15. In some embodiments, the bodywash isapplied more than once; in these cases, the SPF may be cumulative andcan increase with the second wash to, e.g., an average of more than 2,5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 15, 16, 17, 18, 19, 20, 21, 22, 23,24, 25, 30, 35, 40, 45, or more than about 45. In some embodiments thebodywash is applied once per day. In some embodiments, the bodywash isapplied more than once per day, for example, 2, 3, 4, or more than 4times per day. In some embodiments, the bodywash is applied about everyother day. In some embodiments, the body wash is applied about 10, 8, 7,6, 5, 4, 3, 2 or 1 time per week.

In these methods, the active additive, e.g., sunscreen, often does notpenetrate beyond a certain level in the skin, typically due toencapsulation. Thus, in some embodiments of the methods of theinvention, the active additive, e.g., sunscreen, does not penetrate morethan about 10, 20, 25, 30, 35, 40, 45, or 50 microns into the skin withone washing with a bodywash containing the additive. In someembodiments, the active additive, e.g., sunscreen, does not penetratemore than about 10, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100,120, or 150 microns into the skin, even with repeated washings.

In other embodiments the sunscreen or other additive is designed topenetrate into the skin, thus, in these embodiments, the activeadditive, e.g., sunscreen, penetrates to at least about 10, 20, 25, 30,35, 40, 45, or 50 microns into the skin with one washing with a bodywashcontaining the additive. In some embodiments, the active additive, e.g.,sunscreen, penetrates more than about 10, 20, 25, 30, 35, 40, 45, 50,60, 70, 80, 90, 100, 120, or 150 microns into the skin. In someembodiments this penetration occurs with a single washing and rinsing.In some embodiments this penetration occurs with repeated washings andrinsings.

Any additive described herein, e.g., sunscreen additives, generally as acomponent of a bodywash, may be used in the methods of the invention. Insome embodiments, the additive is a non-sunscreen additive and isencapsulated, e.g., in the form of sol-gel microcapsules. In theseembodiments, the additive may be used in combination with a non-bodywashvehicle, such as a skin lotion, gel, cream, and the like, as arewell-known in the art.

While it is ordinarily preferred to use the compositions of the presentinvention in a manner similar to ordinary soap (i.e., wetting,application of composition, rinsing), it is also anticipated that thecomposition may be used by application without wetting followed byremoval through, for example, wiping. This is the case for soaplesscleansers.

C. Business Methods

The invention also encompasses methods of doing business in the field oftopical delivery of cosmeceuticals and the transdermal delivery ofpharmaceuticals using lathering products, including everyday soap andshampoo, as the delivery agents.

Consumers spend more than $30 billion annually on products that takeadvantage of topical and transdermal delivery methods. Despite enormousgrowth in this area, there have been few major innovations. Mostdelivery methods still rely on lotions, creams or patches. By combininga cosmetic or even pharmaceutical regimen with an activity as routine aswashing up or showering, the business methods of the invention capture asignificant share of the topical and transdermal delivery market.Products enable personal care product makers to secure a piece of thegrowing market for cosmeceuticals, like sunscreen, by enhancing existingproduct lines. They will also enable drug makers to offer consumers moreappealing ways to administer prescription and over-the-counterpharmaceuticals

Business methods of the invention encompass a method of doing businesscomprising marketing an additive for use with an existing bodywash,wherein the additive, when combined with the bodywash, causes anadditional effect to the normal effect of the soap or the bodywash. Thebusiness methods include methods involving any of the additivesdescribed herein, including sunscreens, insect repellants, anti-acnemedications, anti-wrinkling agents, deodorants, and all others describedherein In some embodiments, the methods include marketing a sunscreenbenefit agent (additive) for use with a bodywash, e.g., bar and liquidsoaps, and shampoos, to add the benefit of a sunscreen. The sunscreenmay be any one of the sunscreen additives described herein. Thisembodiment is designed to appeal to soap manufacturers looking tobroaden the market for their products among the growing population ofconsumers concerned about skin cancer and wrinkles. Generally, thebenefit agent is marketed as a brand-neutral additive for use withexisting brands. In some cases, a stand-alone brand may be created.

The sunscreen or other benefit agent may be licensed as an additive, inboth liquid and bar soap forms, to personal care product makers of allsizes, to enhance and differentiate their branded product offerings. Thelicense may be exclusive or, preferably, non-exclusive. If exclusive, itmay be exclusive in a defined geographical territory, for a defined timeperiod (often with an option to renew or right of first refusal at theexpiration of the time period), for a defined type of skin care product,or any combination of these. The methods also include supplying one ormore customers with an option to license or buy the additive, generallyfor a defined period of time. As with licenses, such an option may beexclusive or non-exclusive. Alternatively, the sunscreen or otherbenefit agent may be manufactured and supplied to personal care productmakers. A further alternative is to manufacture a stand-alone brand ofsoap/bodywash that includes the additive.

A further component of the business methods of the invention typicallyincludes receiving payment for supplying the additive, license, or thelike, to the customer. It will be appreciated that “payment” may be anyform of consideration, included monetary consideration. Typically,license payments take the form of an up-front payment, royalties,license maintenance fees or some combination thereof. Also included inpayment options are equity in the company receiving the additive or thelicense to the additive. It will be appreciated that any other form ofconsideration may also constitute payment in the business methods of theinvention

The business methods of the invention may further include manufacturingthe additive and/or the additive/bodywash. In some embodiments,different entities perform different aspects; for example, a firstentity may manufacture the additive and a second entity may marketand/or distribute it. In some embodiments, a single entity performs bothmanufacturing and marketing.

Business methods of the invention further include a method including thesteps of: a) designing an additive for use in a personal care product;b) testing the additive for safety and effectiveness in humans; c)arranging for distribution and marketing of the additive. In someembodiments, steps a) and c) are performed by a first entity, typicallya business entity, and step b) is performed by a second entity, such asa business entity or an academic entity. In some or these embodiments,step b) is performed as a joint venture between the two entities.

All publications and patent applications mentioned in this specificationare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually indicated to be incorporated by reference.

It will be apparent to one of ordinary skill in the art that manychanges and modification can be made to the disclosures presented hereinwithout departing from the spirit or scope of the appended claims.

EXAMPLES Example 1

A sunscreen additive for addition to a bodywash was prepared as follows:To 13.7 g water was added 1 g of polyquaternium-4 (CELQUAT-200), 1.5 gmof MOISTUREGUARD, and 12 g of UV PEARLS. The mixture was stirred untiluniform, to produce Phase I. Separately, 1 g of PARSOL 1789 was added to4 g of Octocrylene with heating, and stirred until uniform, to producePhase II. Phase I and Phase II were combined with gentle agitation untiluniform to produce Phase III, a sunscreen additive.

The sunscreen additive of Phase III was added to 64.5 g of SUAVEBodywash and stirred until uniform. Finally, 2.3 g of titanium dioxidewere added with stirring. The final composition was asunscreen/bodywash.

Example 2

The sunscreen/bodywash of Example 1 was tested for SPF capability asfollows: 50 cm² of testing site was wetted with 10 ml of water deliveredwith a syringe. The test sample was applied as per FDA monograph C.F.R.21 to the area. Lather was worked into the subject for 3 minutes toallow the product to absorb into the skin. The area was rinsed after 2additional minutes with 20 ml of water, then the area was patted dry andallowed 15 minutes before exposure to radiation as per FDA monograph.The skin was exposed to UV radiation and the MED was noted and comparedto the MED for skin without treatment. Results are shown in the Tablebelow.

TABLE (Lather Method*) Subject MED/ I MED I MED II STD SPF ID # Sex Hr(Amps) Skin Type J/M² J/M² (8% HMS) Value 46 8676 F 127.8 7.0 II 46.2046.20 4.40 15.00 50 3379 F 126.4 7.0 II 46.20 46.20 4.00 18.00 36 0202 F125.8 7.0 II 46.20 46.20 4.40 21.60 56 2392 F 125.8 7.0 II 46.20 46.204.00 18.00 50 1415 F 125.8 7.0 II 46.20 46.20 4.40 21.60 MEAN (x) 4.2418.84 STANDARD DEV (s) 0.22 2.80 STD. ERROR 0.10 1.25 S.E. % OF MEAN2.36 6.63 N 5 5 MED: Minimal Erythemal Dose I: Intensity of light source

This Example demonstrates that the sunscreen/bodywash enhanced the sunprotection as measured by this protocol, as compared to untreated skin,by an average SPF of over 18.

Example 3

A sunscreen/bodywash is prepared by mixing the following ingredients:0.1 to 7.5 parts by weight of octylmethoxy cinnamate, 0.1 to 6 parts byweight of octyl salicylate, 0.1 to 5 parts by weight of oxybenzone, 1 to10 parts by weight of cationic surfactant, 0.01 to 1 part by weight of aquaternized compound and 0.01 to 1 part by weight of a preservative.

Example 4

A sunscreen/bodywash is prepared by mixing the following ingredients:

-   -   Water 20–65%    -   Polyquat 4 0.01–3.75%    -   Dimethicone 0.01–7%    -   Octylmethoxycinnamate in amorphous silica    -   Petrolatum 0.01–10%    -   Titanium Dioxide 0.01–20%    -   Octocrylene 0.01–10%    -   Parsol 1789(Avobenzone) 0.01–3%    -   Kathon 0.01–2%    -   Bodywash generic 5–99%

While preferred embodiments of the present invention have been shown anddescribed herein, it will be obvious to those skilled in the art thatsuch embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the invention. It should be understoodthat various alternatives to the embodiments of the invention describedherein may be employed in practicing the invention. It is intended thatthe following claims define the scope of the invention and that methodsand structures within the scope of these claims and their equivalents becovered thereby.

1. A bodywash comprising an additive that comprises a sunscreen, wherein, after a single application of the bodywash to skin and rinsing, the skin is protected from sunlight with an average SPF of at least 5 for at least 4 hours after said rinsing.
 2. The bodywash of claim 1, wherein the sunscreen is encapsulated.
 3. The bodywash of claim 2, wherein the sunscreen is encapsulated in sol-gel microcapsules.
 4. The bodywash of claim 2, further comprising a cationic polymer.
 5. The bodywash of claim 4, wherein the cationic polymer is a polyquaternium.
 6. The bodywash of claim 5, wherein the cationic polymer is polyquaternium-4.
 7. The bodywash of claim 4, further comprising a film former.
 8. The bodywash of claim 1, further comprising a non-sunscreen active.
 9. A bodywash comprising an additive that comprises an encapsulated sunscreen, wherein, after a single application of the bodywash to skin and rinsing, the skin is protected from sunlight with an average SPF of at least
 5. 10. The bodywash of claim 9, wherein the sunscreen is encapsulated in a sol-gel microcapsule.
 11. The bodywash of claim 9, further comprising a cationic polymer.
 12. The bodywash of claim 11, wherein the cationic polymer is a polyquaternium.
 13. The bodywash of claim 12, wherein the cationic polymer is polyquaternium-4.
 14. The bodywash of claim 11, further comprising a film former.
 15. The bodywash of claim 9, further comprising a non-sunscreen active.
 16. An bodywash comprising a sunscreen, wherein, after a single application of the bodywash to skin and rinsing, the skin is protected from sunlight with an average SPF of at least
 15. 17. The bodywash of claim 16, wherein the sunscreen is encapsulated.
 18. The bodywash of claim 17, wherein the sunscreen is encapsulated in sol-gel microcapsules.
 19. The bodywash of claim 16, further comprising a cationic polymer.
 20. The bodywash of claim 19, wherein the cationic polymer is a polyquaternium.
 21. The bodywash of claim 20, wherein the cationic polymer is polyquaternium-4.
 22. The bodywash of claim 19, further comprising a film former.
 23. The composition of claim 16, further comprising a non-sunscreen active.
 24. A bodywash comprising an additive that comprises a sunscreen encapsulated in a sol-gel microcapsule and a cationic polymer, wherein, after a single application of the bodywash to skin and rinsing, the skin is protected from sunlight with an average SPF of at least about
 2. 